Systems and Methods for Net Carbon Negative and More Profitable Chemical Production

ABSTRACT

The present invention pertains to processes of, for example, preparing zinc oxide and other substances. In one embodiment an exemplary process pertains to reacting ammonium chloride with zinc oxide to form a zinc chloride, gaseous ammonia, and gaseous water vapor. The zinc chloride may be reacted with sulfuric acid to form a zinc sulfate and hydrochloric acid. The zinc sulfate may be decomposed to produce zinc oxide among other substances.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional application No.62/895,557 filed Sep. 4, 2019 and U.S. provisional application No.63/042,397 filed Jun. 22, 2020. The application also claims priority toU.S. application Ser. No. 16/944,850 filed Aug. 11, 2020. Theapplication also claims priority to U.S. provisional application No.62/890,254 filed Aug. 22, 2020. All applications are incorporated byreference in their entirety.

BACKGROUND AND SUMMARY

Ammonium chloride and ammonium sulfate are produced as low valuebyproducts of chemical processes. Ammonium chloride can be a wasteproduct of sodium bicarbonate or sodium carbonate production processes,such as the Solvay Process. Ammonium chloride and/or ammonium sulfateare produced as chemical byproducts during the recovery or removal ofammonia using acid scrubbing, where ammonia or ammonia species may bescrubbed or removed from ammonia laden gas or liquid streams. Acidscrubbing may use acids which react strongly with ammonia, such assulfuric acid, hydrochloric acid, or nitric acid, to remove ammonia fromgas or liquid streams, which may include, but are not limited to, one ormore or a combination of the following: wastewater, coke oven gases,ammonia-laden freshwater or marine water, urine, feces, biomass,anerobic digestion water, landfill leachate, fertilizer production, orpurge gases.

Ammonium sulfate can also be produced as a byproduct from the followingCO2 conversion or sequestration reaction:

(NH₄)₂CO₃(aq)+CaSO₄(s)

(NH₄)₂SO₄(aq)+CaCO₃(s)

The above reaction may be an advantageous method for sequestering carbondioxide, especially if the ammonia source is renewable or the ammoniacan be economically recovered from the ammonium sulfate. In prior art,ammonium sulfate and/or ammonium chloride is sold as a low-costfertilizer or is discarded. It would be desirable if these and otherwaste or byproducts could be used efficiently in other processes. Itwould be desirable if ammonia could be recovered from these and otherwaste or byproducts in an efficient or effective manner. Advantageously,the processes of the instant application use such byproductscost-effectively and in an ecofriendly manner.

In one embodiment, a process comprises reacting ammonium chloride withzinc oxide to form a zinc chloride, ammonia, and water. The zincchloride is reacted with sulfuric acid to form a zinc sulfate andhydrochloric acid. The zinc sulfate is thermally decomposed to producezinc oxide.

In another embodiment a process comprises reacting sodium chloride withammonia, carbon dioxide, and water to form sodium bicarbonate andammonium chloride. The ammonium chloride is reacted with zinc oxide toform zinc chloride, ammonia, and water. The zinc chloride is thenreacted with sulfuric acid to form zinc sulfate and hydrochloric acid.The zinc sulfate may then be decomposed to produce zinc oxide.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1: Process for producing sodium bicarbonate and ammonium chloridefrom sodium chloride, ammonia, carbon dioxide, and water.

FIG. 2: Process for producing ammonia and hydrochloric acid fromammonium chloride

FIG. 3: Process for producing ammonia and hydrochloric acid fromammonium chloride

FIG. 4: Process for producing ammonia and hydrochloric acid fromammonium chloride

FIG. 5: Process for producing calcium sulfate solid and ammoniumchloride from ammonium sulfate and calcium chloride

FIG. 6: Process for producing sodium bicarbonate and ammonium chloridefrom sodium chloride, ammonia, carbon dioxide, and water.

DETAILED DESCRIPTION OF THE INVENTION

Example Figure Keys

Label Description FIG. 1 Key 1 ‘1’ may comprise sodium chloride input.‘1’ may comprise a solid, or an aqueous solution or a combinationthereof. 2 ‘2’ may comprise mixer or dissolution facilitating device.‘2’ may involve mixing sodium chloride with an ammonium chloride richsolution. In some embodiments, at a temperature less than or equal to acertain temperature range, which may be above 10° C., ammonium chloridemay be less soluble than sodium chloride in water and a portion ammoniumchloride may precipitate upon the dissolution of a sufficientconcentration of sodium carbonate. ‘2’ may be cooled or employ a coolingjacket or a combination thereof. Precipitation of ammonium chloride mayoccur before, during, or after or a combination thereof ‘2’. It may bedesirable for one or more mixer or dissolution facilitating devices tobe initially heated or warm and then cooled to facilitate ammoniumchloride precipitation. ‘2’ may involve cooling, heating, or both. 3 ‘3’may comprise sodium chloride and ammonium chloride. ‘3’ may comprise asolid liquid mixture, which may comprise a liquid phase comprisingsodium chloride rich aqueous solution and a solid phase comprisingammonium chloride. ‘3’ may be transferred to a solid-liquid separationdevice. 4 ‘4’ may comprise a solid-liquid phase separation device and/orprecipitation facilitating device. For example, ‘4’ may comprise acentrifuge, or filter, or rotary filter, or a combination thereof. 5 ‘5’may comprise ammonium chloride. ‘5’ may comprise ammonium chloride at asolid phase. ‘5’ may be transferred to one or more embodiments hereinemploying ammonium chloride, which may include, but are not limited to,processes for converting ammonium chloride into ammonia and/orhydrochloric acid. ‘5’ may be employed for other applications ofammonium chloride, such as applications of ammonium chloride known inthe art. ‘5’ may comprise some residual aqueous solution and/or sodiumchloride and/or sodium bicarbonate and/or other potential contaminants,which may be at least in part removed with additional treatment orseparations, if desired. 6 ‘6’ may comprise an aqueous solution rich insodium chloride and lean in ammonium chloride. 7 ‘7’ may comprise anabsorption or dissolution unit. ‘7’ may comprise an ammonia and/ orwater absorption or dissolution unit. ‘7’ may involve absorbing ordissolving ammonia and/or water into a solution comprising sodiumchloride and/or ammonium chloride. 8 ‘8’ may comprise ammonia and/orwater. ‘8’ may be transferred into an absorption or dissolution unit.‘8’ may be sourced from one or more or a combination of embodimentsherein for generating ammonia. Alternatively, or additionally, ammoniamay be sourced from one or more or a combination of other sources, suchas ammonia sources known in the art. 9 ‘9’ may comprise an aqueoussolution rich in ammonia, rich in sodium chloride, and lean in ammoniumchloride. ‘9’ may be transferred from an ammonia absorption ordissolution step to a sodium bicarbonate formation step. 10 ‘10’ maycomprise an absorption unit or dissolution unit or reactor orprecipitation unit or a combination thereof. ‘10’ may involve absorbingor dissolving carbon dioxide into a solution comprising an aqueoussolution rich in ammonia, rich in sodium chloride, and lean in ammoniumchloride. Said absorption or dissolution of carbon dioxide may result inthe formation of sodium bicarbonate precipitate, or sodium bicarbonate,or ammonium chloride, or ammonium bicarbonate, or ammonium carbonate, ora combination thereof. Said formation of sodium bicarbonate precipitatemay occur before, during, or after, or a combination thereof ‘10’. 11‘11’ may comprise carbon dioxide. ‘11’ may comprise high purity carbondioxide. ‘11’ may comprise carbon dioxide in a gas mixture comprisingother gases in addition to carbon dioxide. ‘11’ may comprise carbondioxide from one or more or a combination of sources. 12 ‘12’ maycomprise a solid-liquid mixture comprising sodium bicarbonate andaqueous ammonium chloride. At least a portion of said sodium bicarbonatemay comprise a solid phase. Said aqueous ammonium chloride may comprisea liquid aqueous phase and may be rich in ammonium chloride. 13 ‘13’ maycomprise a solid-liquid separation device and/or precipitationfacilitating device. For example, ‘13’ may comprise a centrifuge, orfilter, or rotary filter, or a combination thereof. 14 ‘14’ may comprisea sodium bicarbonate at a solid phase. ‘14’ may comprise residualaqueous solution and/or ammonium chloride and/or sodium chloride, whichmay be removed with further treatment or separation, if desired. ‘14’may comprise a valuable product from the present embodiment. 15 ‘15’ maycomprise an ammonium chloride rich aqueous solution. FIGS. 2, 3, 4 Key 1Input ammonium chloride. In ‘1’, ammonium chloride may comprise ammoniumchloride solid, or a gaseous mixture of ammonia and hydrochloric acid,or a combination thereof. Ammonium chloride in ‘1’ may comprise ammoniumchloride recirculated from an interconnected process, which may involvea process which uses ammonia produced by the present embodiment andproduces ammonium chloride, which may comprise ‘1’ in the presentembodiment. For example, ammonium chloride may be sourced from theembodiment shown in FIG. 1, or the embodiment shown in FIG. 5, or theembodiment shown in FIG. 6, or a process for producing sodium carbonate,or a process for producing sodium bicarbonate. Ammonium chloride may besourced from a source described herein, or an ammonium chloride sourcein the art, or a combination thereof. 2 ‘2’ may comprise a mixingdevice, a pulverizing device, a funnel, or a combination thereof. ‘2’may involve mixing ammonium chloride with zinc oxide. 3 ‘3’ may comprisea mixture of ammonium chloride and zinc oxide. 4 ‘4’ may comprise adevice or mechanism for directing or transferring or a combinationthereof a mixture of ammonium chloride and zinc oxide to an appropriatereactor. An appropriate reactor may comprise a reactor undergoingfilling with ammonium chloride and zinc oxide. 5 ‘5’ may comprise amixture of ammonium chloride and zinc oxide being transferred to areactor, such as reactor ‘8’. 6 ‘6’ may comprise a mixture of ammoniumchloride and zinc oxide being transferred to a reactor, such as reactor‘9’. 7 ‘7’ may comprise a mixture of ammonium chloride and zinc oxidebeing transferred to a reactor, such as reactor ‘10’. 8 ‘8’ may comprisea reactor or kiln or a combination thereof. ‘8’ may heat zinc oxide andammonium chloride under conditions to form zinc chloride, ammonia gas,and/ or water vapor. Said reactor may be operated in a batch sequence,in a semi-batch sequence, or continuously, or a combination thereof. Inthe present figure, ‘8’ may be shown operating in a sequence involvingprimarily three steps: 1) filling, 2) reacting, 3) emptying. In FIG. 2,‘8’ is shown filling. In FIG. 3, ‘8’ is shown reacting. In FIG. 4, ‘8’is shown emptying. 9 ‘9’ may comprise a reactor or kiln or a combinationthereof. ‘9’ may heat zinc oxide and ammonium chloride under conditionsto form zinc chloride, ammonia gas, and/ or water vapor. Said reactormay be operated in a batch sequence, in a semi-batch sequence, orcontinuously, or a combination thereof. In the present figure, ‘9’ maybe shown operating in a sequence involving primarily three steps: 1)filling, 2) reacting, 3) emptying. In FIG. 2, ‘9’ is shown reacting. InFIG. 3, ‘9’ is shown emptying. In FIG. 4, ‘9’ is shown filling. 10 ‘10’may comprise a reactor or kiln or a combination thereof. ‘10’ may heatzinc oxide and ammonium chloride under conditions to form zinc chloride,ammonia gas, and/ or water vapor. Said reactor may be operated in abatch sequence, in a semi-batch sequence, or continuously, or acombination thereof. In the present figure, ‘10’ may be shown operatingin a sequence involving primarily three steps: 1) filling, 2) reacting,3) emptying. In FIG. 2, ‘10’ is shown emptying. In FIG. 3, ‘10’ is shownfilling. In FIG. 4, ‘10’ is shown reacting. 11 ‘11’ may comprise gasesgenerated during a reaction to form zinc chloride, ammonia, and/orwater. ‘11’ may comprise ammonia and/or water vapor. ‘11’ may undergofurther treatment, which may include, but is not limited to,condensation of at least a portion of water and/or ammonia. 12 ‘12’ maycomprise gases generated during a reaction to form zinc chloride,ammonia, and/or water. ‘12’ may comprise ammonia and/or water vapor.‘12’ may undergo further treatment, which may include, but is notlimited to, condensation of at least a portion of water and/or ammonia.13 ‘13’ may comprise gases generated during a reaction to form zincchloride, ammonia, and/or water. ‘13’ may comprise ammonia and/or watervapor. ‘13’ may undergo further treatment, which may include, but is notlimited to, condensation of at least a portion of water and/or ammonia.14 ‘14’ may comprise a device or mechanism for directing or transferringor a combination thereof gases exiting one or more or a combination ofreactors. Said gases may comprise ammonia and/or water vapor. 15 ‘15’may comprise ammonia and/or water. ‘15’ may be at a gas, or liquid, orsolid, or a combination thereof state. ‘15’ may be transferred to aninterconnected process, such as, including, but not limited to, one ormore or a combination of the following: a process for producing sodiumcarbonate or sodium bicarbonate, a process herein which producesammonium chloride, or a process which produces ammonium chloride fromammonia. Ammonia may be separated from water in subsequent treatmentsteps. Alternatively, or additionally, ammonia may be dissolved inwater, which may form an ammonium hydroxide solution. At least a portionof ‘15’ may comprise an output from the present embodiment and/or maycomprise a valuable byproduct from the present embodiment. 16 ‘16’ maycomprise zinc chloride reaction product exiting a reactor. ‘16’ may beat a solid phase. 17 ‘17’ may comprise zinc chloride reaction productexiting a reactor. ‘17’ may be at a solid phase. 18 ‘18’ may comprisezinc chloride reaction product exiting a reactor. ‘18’ may be at a solidphase. 19 ‘19’ may comprise a device or mechanism for directing ortransferring or a combination thereof zinc chloride from one or morereactors. ‘19’ may involve transferring said zinc chloride to a reactionstep or reactor which converts said zinc chloride to a thermallydecomposable salt, such as zinc sulfate or zinc nitrate. 20 ‘20’ maycomprise zinc chloride being transferred to a reaction step or reactorwhich converts zinc chloride to a thermally decomposable salt, such aszinc sulfate or zinc nitrate. 21 ‘21’ may comprise a reactor which mixesconverts zinc chloride and sulfur acid into zinc sulfate andhydrochloric acid. 22 ‘22’ may comprise a mixture of zinc sulfate andhydrochloric acid. ‘22’ may comprise a solid-liquid mixture, or ‘22’ maycomprise an aqueous solution, or ‘22’ may comprise a combinationthereof. 23 ‘23’ may comprise one or more or a combination of separationdevices for separating zinc sulfate from hydrochloric acid. Separationdevices may include, but are not limited to, solid-liquid separators,centrifuges, filters, rotary filter, coalesce, evaporators,crystallizers, precipitators, membrane-based processes, coolers,heaters, ion-exchange, electrodialysis, electrolysis, or a combinationthereof. 24 ‘24’ may comprise hydrochloric acid product. ‘24’ maycomprise hydrochloric acid which may exit the process, or undergofurther treatment, or be employed in an interconnected process, or acombination thereof. 25 ‘25’ may comprise zinc sulfate, which may be ata solid or liquid or aqueous or a combination thereof phase. 26 ‘26’ maycomprise a device or mechanism for directing or transferring or acombination thereof zinc sulfate from, for example, one or moreseparators or reactors or a combination thereof, to one or moreappropriate reactors. ‘26’ may involve transferring said zinc sulfate toa reaction step or reactor which converts said zinc sulfate into zincoxide, or sulfur dioxide, or diatomic oxygen, or sulfur trioxide, or acombination thereof. 27 ‘27’ may comprise zinc sulfate being transferredto a reaction step or reactor which converts said zinc sulfate into zincoxide, or sulfur dioxide, or diatomic oxygen, or sulfur trioxide, or acombination thereof. 28 ‘28’ may comprise zinc sulfate being transferredto a reaction step or reactor which converts said zinc sulfate into zincoxide, or sulfur dioxide, or diatomic oxygen, or sulfur trioxide, or acombination thereof. 29 ‘29’ may comprise zinc sulfate being transferredto a reaction step or reactor which converts said zinc sulfate into zincoxide, or sulfur dioxide, or diatomic oxygen, or sulfur trioxide, or acombination thereof. 30 ‘30’ may comprise a reactor or kiln or acombination thereof. ‘30’ may involve thermally decomposing zinc sulfateinto zinc oxide, or sulfur dioxide, or diatomic oxygen, or sulfurtrioxide, or a combination thereof. Zinc oxide may comprise a solidphase product. Sulfur dioxide, or diatomic oxygen, or sulfur trioxide,or a combination thereof may comprise gaseous or liquid products. 31‘31’ may comprise a reactor or kiln or a combination thereof. ‘31’ mayinvolve thermally decomposing zinc sulfate into zinc oxide, or sulfurdioxide, or diatomic oxygen, or sulfur trioxide, or a combinationthereof. Zinc oxide may comprise a solid phase product. Sulfur dioxide,or diatomic oxygen, or sulfur trioxide, or a combination thereof maycomprise gaseous or liquid products. 32 ‘32’ may comprise a reactor orkiln or a combination thereof. ‘32’ may involve thermally decomposingzinc sulfate into zinc oxide, or sulfur dioxide, or diatomic oxygen, orsulfur trioxide, or a combination thereof. Zinc oxide may comprise asolid phase product. Sulfur dioxide, or diatomic oxygen, or sulfurtrioxide, or a combination thereof may comprise gaseous or liquidproducts. 33 ‘33’ may comprise sulfur dioxide, or diatomic oxygen, orsulfur trioxide, or a combination thereof. ‘33’ may be produced from thethermal decomposition of zinc sulfate in kiln or reactor. 34 ‘34’ maycomprise sulfur dioxide, or diatomic oxygen, or sulfur trioxide, or acombination thereof. ‘34’ may be produced from the thermal decompositionof zinc sulfate in kiln or reactor. 35 ‘35’ may comprise sulfur dioxide,or diatomic oxygen, or sulfur trioxide, or a combination thereof. ‘35’may be produced from the thermal decomposition of zinc sulfate in kilnor reactor. 36 ‘36’ may comprise a device or mechanism for directing ortransferring or a combination thereof sulfur dioxide, or diatomicoxygen, or sulfur trioxide, or a combination thereof. ‘36’ may involvetransferring said sulfur dioxide, or diatomic oxygen, or sulfurtrioxide, or a combination thereof to a reaction step or reactor whichmay produce sulfur trioxide or may produce sulfuric acid or acombination thereof. 37 ‘37’ may comprise sulfur dioxide, or diatomicoxygen, or sulfur trioxide, or a combination thereof being transferredto a reaction step or reactor which may produce sulfur trioxide or mayproduce sulfuric acid or a combination thereof. 38 ‘38’ may comprise areactor or reaction step for converting sulfur dioxide and diatomicoxygen into sulfur trioxide. Sulfur dioxide and/or diatomic oxygen maybe converted to sulfur trioxide using one or more or a combination ofmethods known in the art. For example, sulfur dioxide and diatomicoxygen may be contacted with a V₂O₅ catalyst or vanadium oxide catalystunder suitable conditions to form sulfur trioxide as a reaction product.39 ‘39’ may comprise sulfur trioxide. ‘39’ may comprise sulfur trioxidetransferred to a sulfuric acid production process. 40 ‘40’ may comprisewater which may be employed in the production of sulfuric acid fromsulfur trioxide. If desired, water may be recovered from ‘15’ and saidwater may be suitable to be employed as at least a portion of ‘40’. 41‘41’ may comprise a reactor or reaction step for converting sulfurtrioxide into sulfuric acid. ‘41’ may produce sulfuric acid by reactingsulfur trioxide with water under suitable conditions. As with othersteps of the present invention, heat may be recovered during ‘41’. 42‘42’ may comprise sulfuric acid. ‘42’ may comprise sulfuric acidtransferred to a reactor or reaction step involving the conversion ofzinc chloride into zinc sulfate. 43 ‘43’ may comprise zinc oxide. ‘43’may comprise zinc oxide produced from the thermal decomposition of zincsulfate. ‘43’ may comprise zinc oxide transferred to a step or stepsinvolving mixing or reaction with ammonium chloride. 44 ‘44’ maycomprise zinc oxide. ‘44’ may comprise zinc oxide produced from thethermal decomposition of zinc sulfate. ‘44’ may comprise zinc oxidetransferred to a step or steps involving mixing or reaction withammonium chloride. 45 ‘45’ may comprise zinc oxide. ‘45’ may comprisezinc oxide produced from the thermal decomposition of zinc sulfate. ‘45’may comprise zinc oxide transferred to a step or steps involving mixingor reaction with ammonium chloride. 46 ‘46’ may comprise a device ormechanism for directing or transferring or a combination thereof zincoxide from one or more reactors. ‘46’ may involve transferring said zincoxide to a step involving mixing zinc oxide with ammonium chloride orreacting zinc oxide with ammonium chloride or a combination thereof. 47‘47’ may comprise zinc oxide being transferred to a step involvingmixing zinc oxide with ammonium chloride or reacting zinc oxide withammonium chloride or a combination thereof. FIG. 5 Key 1 ‘1’ maycomprise ammonium sulfate. ‘1’ may comprise ammonium sulfate at a solidphase or an aqueous phase. 2 ‘2’ may comprise mixer, or a dissolutionfacilitating device, or a precipitation facilitating device, or acombination thereof. ‘2’ may involve mixing ammonium sulfate with asolution comprising a calcium chloride rich solution. Said mixing ofammonium sulfate with a solution comprising a calcium chloride richsolution may result in the formation of calcium sulfate precipitate andan ammonium chloride rich solution. 3 ‘3’ may comprise a solid-liquidmixture of calcium sulfate solid and an ammonium chloride rich solution.4 ‘4’ may comprise a solid-liquid separation device and/or precipitationfacilitating device. For example, ‘4’ may comprise a centrifuge, orfilter, or rotary filter, or a combination thereof. 5 ‘5’ may comprisecalcium sulfate solid. ‘5’ may comprise residual aqueous solution orother contaminants, which may be removed using further separation ortreatment, if desired. ‘5’ may comprise precipitate gypsum, which maycomprise a valuable byproduct. 6 ‘6’ may comprise an ammonium chloriderich solution. ‘6’ may be at a higher temperature, such as a temperaturegreater than or equal to one or more or a combination of the following:−10° C., or 0° C., or 20° C., or 30° C., or 40° C., or 50° C. 7 ‘7’ maycomprise mixer, or a dissolution facilitating device, or a precipitationfacilitating device, or a combination thereof. ‘7’ may involve coolingan ammonium chloride rich solution to, for example, reduce thesolubility of ammonium chloride and/ or facilitate the precipitation ofammonium chloride. At least a portion of ammonium chloride mayprecipitate before, during, or after or a combination thereof ‘7’. 8 ‘8’may comprise a solid-liquid mixture. ‘8’ may comprise a solid-liquidmixture comprising solid phase comprising ammonium chloride and liquidphase comprising aqueous ammonium chloride lean solution. 9 ‘9’ maycomprise a solid-liquid phase separation device and/or precipitationfacilitating device. For example, ‘4’ may comprise a centrifuge, orfilter, or rotary filter, or a combination thereof. 10 ‘10’ may compriseammonium chloride. ‘10’ may comprise ammonium chloride at a solid phase.‘10’ may comprise residual water and/or other contaminants, which may beremoved with further separation or treatment, if desired. ‘10’ maytransferred to one or more or a combination of embodiments herein whichemploy ammonium chloride, which may be interconnected. ‘10’ may employedin other applications, including applications of ammonium chloride knownin the art. 11 ‘11’ may comprise an ammonium chloride solution. ‘11’ maycomprise an ammonium chloride lean aqueous solution. ‘11’ may be at alower temperature, such as a temperature less than or equal to one ormore or a combination of the following: −10° C., or 0° C., or 20° C., or30° C., or 40° C., or 50° C. 12 ‘12’ may comprise a heat exchanger orheat source or heating device or heating method or a combinationthereof. ‘12’ may be employed to pre-heat or heat an ammonium chloridelean aqueous solution. 13 ‘13’ may comprise a pre-heated or heatedsolution comprising ammonium chloride lean aqueous solution. 14 ‘14’ maycomprise mixer, or a dissolution facilitating, or a combination thereof.‘14’ may involve dissolving calcium chloride in an ammonium chloridelean aqueous solution. 15 ‘15’ may comprise calcium chloride. ‘15’ maycomprise calcium chloride solid or a calcium chloride solution or acombination thereof. 16 ‘16’ may comprise a calcium chloride rich,ammonium chloride rich aqueous solution. ‘16’ may be at a highertemperature, such as a temperature greater than or equal to one or moreor a combination of the following: −10° C., or 0° C., or 20° C., or 30°C., or 40° C., or 50° C. FIG. 6 Key 1 ‘1’ may comprise sodium chlorideinput. ‘1’ may comprise a solid, or an aqueous solution, or acombination thereof. 2 ‘2’ may comprise mixer or dissolutionfacilitating device. ‘2’ may involve mixing sodium chloride with wateror an aqueous solution. 3 ‘3’ may comprise sodium chloride. ‘3’ maycomprise an aqueous solution rich in sodium chloride. 4 ‘4’ may comprisean absorption or dissolution unit. ‘4’ may comprise an ammonia and/ orwater absorption or dissolution unit. ‘4’ may involve absorbing ordissolving ammonia and/or water into a solution comprising sodiumchloride. 5 ‘5’ may comprise ammonia and/or water. ‘5’ may betransferred into an absorption or dissolution unit. ‘5’ may be sourcedfrom one or more or a combination of embodiments herein for generatingammonia. Alternatively, or additionally, ammonia may be sourced from oneor more or a combination of other sources, such as ammonia sources knownin the art. 6 ‘6’ may comprise an aqueous solution rich in ammonia andrich in sodium chloride. ‘6’ may be transferred from an ammoniaabsorption or dissolution step to a sodium bicarbonate formation step. 7‘7’ may comprise an absorption unit or dissolution unit or reactor orprecipitation unit or a combination thereof. ‘7’ may involve absorbingor dissolving carbon dioxide into a solution comprising an aqueoussolution rich in ammonia and rich in sodium chloride. Said absorption ordissolution of carbon dioxide may result in the formation of sodiumbicarbonate precipitate, or sodium bicarbonate, or ammonium chloride, orammonium bicarbonate, or ammonium carbonate, or a combination thereof.Said formation of sodium bicarbonate precipitate may occur before,during, or after, or a combination thereof ‘7’. 8 ‘8’ may comprisecarbon dioxide. ‘8’ may comprise high purity carbon dioxide. ‘8’ maycomprise carbon dioxide in a gas mixture comprising other gases inaddition to carbon dioxide. ‘8’ may comprise carbon dioxide form one ormore or a combination of sources. 9 ‘9’ may comprise a solid-liquidmixture comprising sodium bicarbonate and aqueous ammonium chloride. Atleast a portion of said sodium bicarbonate may comprise a solid phase.Said aqueous ammonium chloride may comprise a liquid aqueous phase andmay be rich in ammonium chloride. 10 ‘10’ may comprise a solid-liquidseparation device and/or precipitation facilitating device. For example,‘10’ may comprise a centrifuge, or filter, or rotary filter, or acombination thereof. 11 ‘11’ may comprise a sodium bicarbonate at asolid phase. ‘11’ may comprise residual aqueous solution and/or ammoniumchloride and/or sodium chloride, which may be removed with furthertreatment or separation, if desired. ‘11’ may comprise a valuableproduct from the present embodiment. 12 ‘12’ may comprise an ammoniumchloride rich aqueous solution. 13, 14, May comprise one or more or acombination of systems for separating ammonium 15, 17 chloride from anaqueous solution. May comprise one or more or a combination ofseparation systems, methods, and/or devices described herein or known inthe art. 16 ‘16’ may comprise ammonium chloride. ‘16’ may compriseammonium chloride at a solid phase. ‘16’ may be transferred to one ormore embodiments herein employing ammonium chloride, which may include,but are not limited to, processes for converting ammonium chloride intoammonia and/or hydrochloric acid. ‘16’ may be employed for otherapplications of ammonium chloride, such as applications of ammoniumchloride known in the art. ‘16’ may comprise some residual aqueoussolution and/or sodium chloride and/or sodium bicarbonate and/or otherpotential contaminants, which may be at least in part removed withadditional treatment or separations, if desired. 18 ‘18’ may comprisewater, or a solution comprising ammonium chloride, or a combinationthereof.

Example Definitions

Free Ammonia: Free ammonia may comprise ammonia which may be unreactedor unaltered. Free ammonia may comprise gaseous, liquid, or solidammonia. Free ammonia may comprise ammonia dissolved in water or one ormore or a combination of solvents.

Lean: ‘Lean’ may represent the concentration of a reagent relative tothe concentration of the same reagent at another point in a process.‘Lean’ represents a relatively lower concentration.

Rich: ‘Rich’ may represent the concentration of a reagent relative tothe concentration of the same reagent at another point in a process.‘Rich’ represents a relatively greater concentration.

Filling: In some embodiments, ‘filling’ may involve the addition ofreactants to a reactor.

Reacting: In some embodiments, ‘reacting’ may involve reactants in areactor undergoing one or more or a combination of reactions which mayresult in one or more or a combination of reaction products.

Emptying: In some embodiments, ‘emptying’ may involve the removal ortransfer of one or more or a combination of products from one or more ora combination of reactors.

Low Carbon or Net Carbon Emission Negative Ammonia Production and/orSodium Bicarbonate or Sodium Carbonate Production

Background

Ammonium chloride and ammonium sulfate are produced as low valuebyproducts of chemical processes. Ammonium chloride can be a wasteproduct of sodium bicarbonate or sodium carbonate production processes,such as the Solvay Process. Ammonium chloride and/or ammonium sulfateare produced as chemical byproducts during the recovery or removal ofammonia using acid scrubbing, where ammonia or ammonia species may bescrubbed or removed from ammonia laden gas or liquid streams. Acidscrubbing may use acids which react strongly with ammonia, such assulfuric acid, hydrochloric acid, or nitric acid, to remove ammonia fromgas or liquid streams, which may include, but are not limited to, one ormore or a combination of the following: wastewater, coke oven gases,ammonia-laden freshwater or marine water, urine, feces, biomass,anerobic digestion water, landfill leachate, fertilizer production, orpurge gases.

Ammonium sulfate can also be produced as a byproduct from the followingCO2 conversion or sequestration reaction:

(NH₄)₂CO₃(aq)+CaSO₄(s)

(NH₄)₂SO₄(aq)+CaCO₃(s)

The above reaction may be an advantageous method for sequestering carbondioxide, especially if the ammonia source is renewable or the ammoniacan be economically recovered from the ammonium sulfate.

In prior art, ammonium sulfate and/or ammonium chloride is sold as alow-cost fertilizer or is discarded.

In sodium carbonate or sodium bicarbonate production, such as the Solvayprocess, ammonia is recovered from the ammonium chloride byproduct byreacting the ammonium chloride with calcium oxide or calcium hydroxide.Both calcium oxide and calcium hydroxide are produced in the very energyand CO₂ emission intensive process of calcining, where CaCO₃ is heatedto an elevated temperature and decomposed into CaO and CO₂. Due to thenature of the chemistry of calcining, it emits significant amounts ofCO₂ not only due to its thermal energy demands (which are generallypowered by the burning of coal), but also or mostly due to the CO₂directly released from the decomposition of CaCO₃ into CaO and CO₂. Inaddition to the high cost, energy and CO₂ emission intensive nature ofrecovering ammonia by reacting it with calcium oxide, the resultingcalcium chloride byproduct is also generally a waste product, usuallydisposed by discarding into the ocean.

Summary of Some Example Embodiments

An example present embodiment may involve converting ammonium chlorideand/or ammonium sulfate, which may be waste products or low cost, intovaluable free ammonia (for example: ammonium hydroxide solution orgaseous ammonia or anhydrous ammonia). Free ammonia may be used within achemical process (for example, which may include, but is not limited to,a process for production sodium bicarbonate or sodium carbonate) or soldor used various applications for ammonia. The present embodiment mayalso be employed in small-scale ammonia production, or medium scaleammonia production, or large scale ammonia production.

It is important to note Embodiment 1, for example, may consume 233kJ/mol of heat to produce a mole of ammonia; compared to 410.6 kJ/moleof heat to produce a mole of ammonia from natural gas using theHaber-Bosch Process. It is important to note the present embodiments maynot require a solid catalyst to operate, which is a unique distinctionbecause other ammonia production processes require solid catalysts. Itis important to note the present embodiments may be suited for producingvalue from excess or low-cost natural gas or flare gases by using theheat from flaring to produce valuable ammonia and hydrochloric acid.Ammonia may be compressed or liquified and may be sold, if desired.

The hydrochloric acid is a valuable byproduct. For example, hydrochloricacid may be employed in the production of chlorinated chemicals orpolymers, such as PVC. For example, hydrochloric acid which is arequired chemical in some oil & gas production operations. The presentembodiments, for example, when employed on oil & gas drilling sites maycomprise ‘hydrochloric acid generators’. Ammonium chloride is mucheasier and lower cost to ship than concentrated hydrochloric acid. Theammonia product produced by the present embodiment may be, for example,transported and/or sold to nearby farms and/or used in otherapplications requiring ammonia. For an upstream oil productionoperation, the present embodiments may transform two loss drivingcomponents of their business (gas flaring and purchasing hydrochlorideacid) into a profit driver for their business (use of flare gas heat topower simultaneous ammonia and hydrochloride acid, wherein hydrochloricacid is consumed onsite and ammonia is sold and/or used onsite). It maybe desirable to convert ammonia into other chemicals, which may include,but are not limited to, urea, chloramine, amines, polymers, methylamine,ethylamine, or other ammonia derivatives, or a combination thereof.

Example Embodiment 1 (NH₄Cl is the Starting Feedstock)

-   1) 2NH₄Cl(s)+ZnO(s)    2NH₃(g)+ZnCl₂(s)+H₂O(g) (+238.66 kJ/mol; +116.33 kJ/mol of NH₃; 210°    C.)-   2) ZnCl₂(s)+H₂SO₄(aq)    ZnSO₄(s)+2HCl(aq) (−83 kJ/mol; −41.5 kJ/mol of NH₃)-   3) ZnSO₄(s)    ZnO(s)+SO₃(g) (+235.14 kJ/mol; +117.57 kJ/mol of NH₃; 920-980° C.)    -   Note: ZnSO₄(s)        ZnO(s)+SO₂(g)+½O₂ (g) (Alternative Reaction; if desired, O₂ may        be reacted with SO₂ to produce SO₃ before reaction ‘(4)’, which        may be facilitated by, for example, a catalyst)-   4) SO₃(g)+H₂O(l)    H₂SO₄(l) (−170 kJ/mol)

Inputs Outputs 2 NH₄Cl(s) 2 NH₃(g) Heat 2 HCl(aq) H₂O H₂O (althoughwater may not be net (although water may not be net consumed in process,HCl product produced in process, HCl product may require additionalwater in may require additional water in aqueous phase relative toH₂SO₄) aqueous phase relative to H₂SO₄. The water may be added during orafter the production of HCl and/ or separation of HCl from zinc sulfateor zinc chloride.)

Reaction 1 Further Description and Proof:

Reaction 1 may involve reacting ammonium chloride and zinc oxide at arelatively elevated temperature to form zinc chloride, water vapor, andammonia gas. The reaction may involve decomposing ammonium chloride andpassing the resulting gas mixture over heated or unheated zinc oxide.The reaction may involve heating a mixture of ammonium chloride (whichmay be, at least initially, at a solid phase) and zinc oxide (which maybe at a solid phase) and forming zinc chloride, ammonia gas, andaccording to Reaction 1. It may be preferred to react a mixture ofammonium chloride and zinc oxide because the solid mixture has beenshown to produce reaction products with lower temperature requirement(210° C. for mixture vs. 338° C. for ammonium chloride alone) and lowerheat input requirement (+116.33 kJ/mol NH₃ for mixture vs. +228.55kJ/mole NH₃ for ammonium chloride alone). An embodiment of the reactionshown in reaction 1 has been demonstrated in literature in the article‘Reaction of zinc oxide with ammonium chloride’ by Borisov et al.Borisov et al found the reactants initially form ammonium chlorozincates((NH₄)₃ZnCl₄) at 150° C., with the evolution of NH₃(g) and H₂O(g).Borisov et al found the mixture of ammonium chloride and zinc oxidecompletely converts into products shown in reaction 1 at about 210° C.Borisov et al found a stoichiometric amount of NH₃ formed and thepresence of zinc did not cause the NH₃ to decompose.

The present reaction may be conducted in a low diatomic oxygenatmosphere or environment. Low diatomic oxygen may involve a volumetricconcentration of diatomic oxygen less than 20 vol %, or less than 19 vol%, or less than 18 vol %, or less than 17 vol %, or less than 19 vol %,or less than 19 vol %, or less than 19 vol %, or less than 19 vol %, orless than 19 vol %, or less than 19 vol %, or less than 19 vol %, orless than 19 vol %, or less than 19 vol %, or less than 19 vol %, orless than 19 vol %, or less than 19 vol %. Low diatomic oxygenconcentration may involving filling a vessel or container with ammoniumchloride and zinc oxide such that less than 10%, or less than 20%, orless than 30%, or less than 40%, or less than 50%, or less than 60%, orless than 70%, or less than 80%, or less than 90%, or a combinationthereof of the space in said vessel or container is occupied by oxygenor a gas comprising oxygen. Low diatomic oxygen concentration mayinvolve ensuring the total mass of ammonia in a reactor or mass ofammonium chloride in a reactor or the total mass of ammonia in the formof ammonium chloride in a reactor exceeds the total mass of diatomicoxygen gas in said reactor by at least 2× or 200%, or 3× or 300%, or 4×or 400%, or 5× or 500%, or 6× or 600%, or 7× or 700%, or 8× or 800%, or9× or 900%, or 10× or 1,000%, or 25× or 2,500%, or 50× or 5,000%, or100× or 10,000%, or 200× or 20,000%, or a combination thereof.

It is important to note that zinc oxide may be recycled internally fromReaction 3 to Reaction 1.

It is important to note metals other than or in addition to zinc may beemployed, which may include, but are not limited to, one or more or acombination of the following: iron, lead, copper, cobalt, nickel,manganese, chromium, silver, scandium, vanadium, titanium, aluminum,magnesium, calcium, sodium, potassium, Yttrium, Zirconium, Niobium,Molybdenum Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium,Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold,Mercury, Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium,Meitnerium, Ununnilium, Unununium, or Ununbium.

Reaction 2 Further Description and Proof:

Reaction 2 may involve reacting zinc chloride with sulfuric acid formzinc sulfate and hydrochloric acid. The enthalpy of Reaction 2 may bestrongly exothermic and favorable and sulfuric acid may be a strongeracid than hydrochloric acid. Reaction 2 may require cooling. Saidcooling may involve recovering heat. Recovered heat may be employed tofacilitate removal or distillation of excess water or separate residualzinc sulfate or zinc chloride from hydrochloric acid. Depending on theconcentration of sulfuric acid, zinc chloride may be placed insufficient water to ensure there is enough water for the producthydrochloric acid to fully dissolve and form hydrochloric acid, ashydrochloric acid may require stoichiometrically more water thansulfuric acid to remain in solution. Alternatively, or additionally, aportion of hydrochloric acid may form as a gas, and may be condensed orrecovered or converted into an aqueous solution or a combinationthereof. Zinc chloride or zinc sulfate may be present primarily at thesolid phase due to, for example, limited amount of relative water and/orthe salting-out effects of HCl or H₂SO₄ in solution. Residual zincchloride or zinc sulfate may comprise, including, but not limited to,one or more or a combination of the following: a membrane-based process,a solid membrane, distillation, electrodialysis, ion exchange,crystallization, crydesalination, freezing desalination, coolingprecipitation, precipitation, salting-out′, or a common-ion effect.

Reaction 3 Further Description and Proof:

Reaction 3 may involve decomposing zinc sulfate into zinc oxide andsulfur trioxide or sulfur dioxide and O₂ or both. According to ‘Kineticsof the Thermal Decomposition of Zinc Sulfate’ by Ibanez et al, zincsulfate decomposes into zinc oxide and sulfur trioxide or sulfur dioxideor O₂ or a combination thereof starting at about 920° C. Zinc oxide maybe transferred or employed or both to Reaction 1 and sulfur trioxide orsulfur dioxide or O₂ or a combination thereof may be employed inReaction 4.

Reaction 4 Further Description and Proof:

Reaction 4 may involve the formation of sulfuric acid from sulfurtrioxide or sulfur oxides which may be converted into sulfur trioxide orsulfuric acid. Reaction 4 is well known in industry to produce sulfuricacid and may be conducted using one or more or a combination of methodsfor producing sulfuric acid in the art. Reaction 4 is highly exothermicand heat from the reaction may be recovered as, for example, steam. Itmay be possible to employ heat from Reaction 4 to power a portion of thethermal duty of Reaction 1. Sulfuric acid product may be employed inReaction 2.

Heat from reaction 4 may be utilized to produce steam or heat producedmay supplement heat requirements of reaction ‘(1)’.

Note: One or more reaction steps may be conducted in separate locationsor separate facilities from one or more other reactions steps ifdesired. It may be desirable to conduct certain reactions where certainfacilities exist. It may be desirable to conduct certain reactions wherecertain economic factors (for example: cost of energy or availability offeedstocks or market/application locations) are relatively morefavorable. If desired, reactions may be split into one or moresub-reactions. Additional treatment steps, such as water addition orremoval or membrane base purification or precipitation or cooling orheating, may be conducted between or during reaction steps.

Note: In the present example embodiment, it may be desirable forammonium sulfate (if, for example, ammonium sulfate is a low-costfeedstock for ammonia) to be converted into ammonium chloride, forexample, by reacting it with calcium chloride or other low cost chloridesalt. For example, the following reaction may be employed:

(NH₄)₂SO₄(aq)+CaCl₂)(aq)

2NH₄Cl(aq)+CaSO₄(s)

The CaSO₄ solid may be sold or used, for example, as Gypsum orprecipitated Gypsum.

As with other reactions described herein, it is important to note theabove reaction to convert (NH₄)₂SO₄(aq) into 2NH₄Cl(aq) may be conductedin a different location from one or more other reactions in the presentembodiments, if desired. Alternatively, or additionally, reactions maybe conducted in the same location or facility.

Note: It is important to note the present embodiments may consume lessenergy in their endothermic reaction steps than is required during theproduction of ammonia from natural gas. The production of ammonia fromnatural gas (not including the additional energy required to separatenitrogen and compress gases and ammonia) requires 410.625 kJ/mol of NH₃produced according to the following equations:

Energetic Value of Methane in Natural Gas (energetic value ofmethane→CO₂ if not transformed into CO₂ using steam reforming and WGS):

CH₄(g)+O₂(g)

CO₂(g)+H₂O(g) (−889 kJ/mol)  (1)

Steam Reforming Reaction Heat Input Required:

CH₄(g)+H₂O(g)

CO(g)+3H₂(g) (+206 kJ/mol, 700-1100° C.)  (2)

Water-Gas Shift Reaction:

CH₄(g)+H₂O(g)

CO(g)+3H₂(g) (−41 kJ/mol, 200-250° C.)  (3)

Ammonia Production Reaction:

1.5H₂(g)+0.5N₂(g)

NH₃(g) (−45.9 kJ/mol)  (4)

Combined Enthalpies of Heat Consuming or Lost Energy Value Steps—‘(1)’and ‘(2)’:

206 kJ/mol+889 kJ/mol=1095 kJ/mol  (5)

Combined Enthalpies of Heat Consuming or Lost Energy Value Steps—‘(1)’and ‘(2)’—on a per Mole NH₃ Produced:

(6) 1095 kJ/mol*1.5/4=410.625 kJ/mol NH₃ Produced

For example, the endothermic reactions of Example Embodiment 1 consume233 kJ per mole of NH₃ produced, which is 177 kJ or 43% less energy thanis required to produce ammonia using the Haber Bosch Process with anatural gas feedstock. It is also important to note that the reactionsin Example Embodiment 1 operate at lower temperatures, there are fewertotal reactions, and there is no energy requirement for compression(which was not included in the 410.625 kJ energy value for NH₃production in Haber Bosch Process with natural gas feedstock). ExampleEmbodiment 1 may also not require expensive catalysts, which arerequired in the Haber Bosch Process, and/or also may not require highpurity gaseous feedstocks, which are also required in the Haber BoschProcess.

Example Embodiment 2 ((NH₄)₂SO₄ and CaCl₂) are the starting feedstocks)

(1) (NH₄)₂SO₄(aq)+CaCl₂(aq)

2NH₄Cl(aq)+CaSO₄(s)

(2) 2NH₄Cl(aq) may be concentrated using FO with CaCl₂ as draw solutionand the 2NH₄Cl(aq) may be precipitated as 2NH₄Cl(s). ‘2)’ comprise acycle wherein (a) NH₄Cl(aq) is mildly heated; and/or (b) concentratedusing forward osmosis with CaCl₂ draw solution; and/or (c) concentratedNH₄Cl(aq) may be cooled to precipitate a portion of the NH₄Cl; and/or(d) the remaining NH₄Cl(aq) solution separated from the NH₄Cl(s)precipitate may be mixed with incoming solution and/or returned to step(a). NH₄Cl(s) precipitate may be transferred to reaction

(3) Because CaCl₂ is deliquescent in contact with air (absorbs waterfrom the air) it may be desirable for the CaCl₂(aq) draw solution tocomprise CaCl₂(s) which has absorbed water from the air to formconcentrated CaCl₂(aq) brine. In some embodiments, it may be desirablefor NH₄Cl(s) to be formed by distillation of a portion of water andcooling crystallization or precipitation of NH₄Cl(s) from an NH₄Cl(aq)solution. In some embodiments, it may be desirable for NH₄Cl(s) to beformed by solventing-out′ NH₄Cl(s) from an NH₄Cl(aq) solution using aregenerable water soluble organic solvent, such as a volatile organicsolvent or a liquid-liquid phase transition organic solvent.

-   1) 2NH₄Cl(s)+ZnO(s)    2NH₃(g)+ZnCl₂(s)+H₂O(g) (+238.66 kJ/mol; +116.33 kJ/mol of NH₃; 210°    C.)-   2) ZnCl₂(s)+H₂SO₄(aq)    ZnSO₄(s)+2HCl(aq) (−83 kJ/mol; −41.5 kJ/mol of NH₃)-   3) ZnSO₄(s)    ZnO(s)+SO₃(g) (+235.14 kJ/mol; +117.57 kJ/mol of NH₃; 920-980° C.)    -   Note: ZnSO₄(s)        4ZnO(s)+SO₂(g)+½O₂ (g) (Alternative Reaction; if desired O₂ may        be reacted with SO₂ to produce SO₃ before reaction ‘(6)’ using,        if desired, a catalyst)-   4) SO₃(g)+H₂O (l)    H₂SO₄(l) (−170 kJ/mol, can be utilized to produce steam or heat    produced may supplement heat requirements of reaction ‘(3)’,    although this heat recovery not required and, for purposes of being    conservative, the heat recovery is not included in energy    consumption calculations)

Inputs Outputs (NH₄)₂SO₄ 2 NH₃(g) CaCl₂ CaSO₄ Heat 2 HCl(aq) H₂O H₂O

Reaction 1 Further Description and Proof:

Ammonium sulfate solid or aqueous and calcium chloride may be mixed toform ammonium chloride aqueous, ammonium chloride solid, calcium sulfatesolid, minimal concentrate of aqueous calcium sulfate (due to minimalsolubility), or a combination thereof. Calcium sulfate solid may formdue to insolubility or relatively low solubility in water. Calciumsulfate solid may form in a step prior to the formation or generation ofammonium chloride solid. Calcium sulfate solid may be separated prior tofurther processing of the remaining solution to produce ammoniumchloride solid.

Reaction 2 Further Description and Proof:

CaCl₂ may have a greater osmotic pressure and/or higher solubility inwater than NH₄Cl at their saturated concentration in water, which mayenable using CaCl₂ input as a draw solution to concentrate remainingNH₄Cl(aq) using forward osmosis (FO). After concentrating, NH₄Cl(aq) maybe cooled, which may result in the precipitation of a portion ofNH₄Cl(s). The remaining solution, which may be lean in NH₄Cl(aq), may beconcentrated using CaCl₂ draw solution, which may occur in one or moreadditional cycles before other NH₄Cl(aq) concentrating and/or NH₄Cl(s)precipitation steps. Alternatively, or additionally, NH₄Cl(aq) may beconcentrated and/or NH₄Cl(s) may be separated using one or more or acombination of the following: cryodesalination, freezing desalination,anti-solvent precipitation, regenerable anti-solvent precipitation,solventing-out, cooling precipitation, distillation, common-ion effect,or other separations described herein.

Alternatively to FO, the NH₄Cl may be concentrated by using thedifference in partial vapor pressure of water over NH₄Cl vs. CaCl₂)solution, which may be conducted using, for example, including, but notlimited to, one or more or a combination of the following: carrier gasdistillation, carrier gas evaporation, vapor gas membrane,pervaporation, membrane distillation, distillation, mechanical vaporcompression distillation, vacuum distillation, headspace water vapor gastransfer, stripping gas water vapor transfer, or distillation.

It is important to note that alternatives to FO or other membrane-basedprocesses may be beneficial because residual CaSO₄ (which dissolves atlow concentrations in water due to limited but existent solubility) mayscale membranes. In some embodiments, distillation of a portion waterand/or crystallization or precipitation of ammonium chloride may beconducted.

In some embodiments, ammonium sulfate may be directly added to asolution comprising ammonium chloride and calcium chloride, which mayresult in the formation of calcium sulfate precipitate. Some embodimentsmay conduct said ammonium sulfate addition step at warmer temperatures,such as, greater than 0° C., or 10° C., or 20° C., or 30° C., or 40° C.,or 50° C., or 60° C., or 70° C., or 80° C., or 90° C. Calcium sulfateprecipitate may be separated form the remaining solution. The remainingsolution may be cooled, which may result in the precipitation of atleast a portion of ammonium chloride solid. Said ammonium chloride solidmay be separated. The remaining solution, which may be ‘lean’ inammonium chloride, may be mixed with input calcium chloride, which mayproduce a solution comprising ammonium chloride and calcium chloride.Said solution may be transferred to the first step of the presentembodiment of ‘Reaction 1’ and/or ‘Reaction 2’. The present embodimentmay comprise a combination of ‘Reaction 1’ and ‘Reaction 2’.

In an example embodiment, (a) ammonium sulfate solid may be mixed with acalcium chloride—ammonium chloride solution, resulting in the formationof additional ammonium chloride from the ammonium sulfate and calciumsulfate precipitate. To prevent ammonium chloride from precipitating atthe same time as calcium sulfate, the concentration of the resultingmore concentrated ammonium chloride solution may desirably be less thanthe maximum solubility or saturation concentration of ammonium chloridein solution at the temperature which the calcium sulfate precipitatingreaction is conducted. (b) Calcium sulfate precipitate may be separatedand may be further washed to, for example, remove any residual ammoniumchloride. (c) The remaining concentrated ammonium chloride solutionafter calcium sulfate precipitation removal may undergo furthertreatment to facilitate the precipitation of a portion of the ammoniumchloride. For example, said treatment may involve systems and methodsfor precipitating salts from solutions, which may include, but are notlimited to: cooling precipitation, antisolvent precipitation, thermallyswitchable antisolvent precipitation, solventing out, salting out, or acombination thereof (d) Precipitated ammonium chloride may be separatedand transferred to Reaction 3. (e) The remaining ammonium chloridesolution following ammonium chloride precipitation and precipitateseparation may be mixed with calcium chloride, forming an ammoniumchloride—calcium chloride solution. To prevent ammonium chlorideprecipitation or facilitate calcium chloride dissolution during thisstep, the solution may be heated before or during calcium chloridedissolution and/or any antisolvents which may have been added may beremoved. The resulting ammonium chloride—calcium chloride solution maybe transferred to step ‘(a)’.

Reaction 1 and/or Reaction 2 may comprise one or more or a combinationof the systems and methods described thereof or herein.

Reaction 3 Further Description and Proof:

Reaction 3 may involve reacting ammonium chloride and zinc oxide at arelatively elevated temperature to form zinc chloride, water vapor, andammonia gas. The reaction may involve decomposing ammonium chloride andpassing the resulting gas mixture over heated or unheated zinc oxide.The reaction may involve heating a mixture of ammonium chloride (whichmay be, at least initially, at a solid phase) and zinc oxide (which maybe at a solid phase) and forming zinc chloride, ammonia gas, andaccording to Reaction 3. It may be preferred to react a mixture ofammonium chloride and zinc oxide because the solid mixture has beenshown to produce reaction products with lower temperature requirement(210° C. for mixture vs. 338° C. for ammonium chloride alone) and lowerheat input requirement (+116.33 kJ/mol NH₃ for mixture vs. +228.55kJ/mole NH₃ for ammonium chloride alone). An embodiment of the reactionshown in Reaction 3 has been demonstrated in literature in the article‘Reaction of zinc oxide with ammonium chloride’ by Borisov et al.Borisov et al found the reactants initially form ammonium chlorozincates((NH₄)₃ZnCl₄) at 150° C., with the evolution of NH₃(g) and H₂O(g).Borisov et al found the mixture of ammonium chloride and zinc oxidecompletely converts into products shown in reaction 1 at about 210° C.Borisov et al found a stoichiometric amount of NH₃ formed and thepresence of zinc did not cause the NH₃ to decompose.

It is important to note that zinc oxide may be recycled internally fromReaction 5 to Reaction 3.

It is important to note metals other than or in addition to zinc may beemployed, which may include, but are not limited to, one or more or acombination of the following: iron, lead, copper, cobalt, nickel,manganese, chromium, silver, scandium, vanadium, titanium, aluminum,magnesium, calcium, sodium, potassium, Yttrium, Zirconium, Niobium,Molybdenum Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium,Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold,Mercury, Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium,Meitnerium, Ununnilium, Unununium, or Ununbium.

Reaction 4 Further Description and Proof:

Reaction 4 involves reacting zinc chloride with sulfuric acid form zincsulfate and hydrochloric acid. The enthalpy of Reaction 4 may bestrongly exothermic and favorable and sulfuric acid may be a strongeracid than hydrochloric acid. Reaction 4 may require cooling. Saidcooling may involve recovering heat. Recovered heat may be employed tofacilitate removal or distillation of excess water or separate residualzinc sulfate or zinc chloride from hydrochloric acid. Depending on theconcentration of sulfuric acid, zinc chloride may be placed insufficient water to ensure there is enough water for the producthydrochloric acid to fully dissolve and form hydrochloric acid, ashydrochloric acid may require stoichiometrically more water thansulfuric acid to remain in solution. Alternatively, or additionally, aportion of hydrochloric acid may form as a gas, and may be condensed orrecovered or converted into an aqueous solution or a combinationthereof. Zinc chloride or zinc sulfate may be present primarily at thesolid phase due to, for example, limited amount of relative water and/orthe salting-out effects of HCl or H₂SO₄ in solution. Residual zincchloride or zinc sulfate may comprise a membrane-based process, a solidmembrane, distillation, electrodialysis, ion exchange, crystallization,cryodesalination, freezing desalination, cooling precipitation,precipitation, ‘salting-out’, common-ion effect, or a combinationthereof.

Reaction 5 Further Description and Proof:

Reaction 5 involves decomposing zinc sulfate into zinc oxide and sulfurtrioxide or sulfur dioxide and O₂ or a combination thereof. According to‘Kinetics of the Thermal Decomposition of Zinc Sulfate’ by Ibanez et al,zinc sulfate decomposes into zinc oxide and sulfur trioxide or sulfurdioxide or O₂ or a combination thereof starting at about 920° C. Zincoxide may be transferred or employed or both to Reaction 3 and sulfurtrioxide or sulfur dioxide or O₂ or a combination thereof may beemployed in Reaction 6.

Reaction 6 Further Description and Proof:

Reaction 6 may involve the formation of sulfuric acid from sulfurtrioxide or sulfur oxides which may be converted into sulfur trioxide orsulfuric acid. Reaction 6 is well known in the art to produce sulfuricacid and may be conducted using one or more or a combination of methodsfor producing sulfuric acid in the art. Reaction 6 is highly exothermicand heat from the reaction may be recovered as, for example, steam. Itmay be possible to employ heat from Reaction 6 to power a portion of thethermal duty of Reaction 1. Sulfuric acid product may be employed inReaction 4.

Example Embodiment 3: Carbon Negative Sodium Carbonate and/or SodiumBicarbonate Production

Background: Sodium carbonate and sodium bicarbonate are produced byeither mining or the Solvay process. The Solvay process produces over75% of the world's sodium carbonate today.

In the Solvay process, ammonia is recovered from the ammonium chloridebyproduct by reacting the ammonium chloride with calcium oxide orcalcium hydroxide. Both calcium oxide and calcium hydroxide are producedin the very energy and CO₂ emission intensive process of calcining,where CaCO₃ is heated to an elevated temperature and decomposed into CaOand CO₂. Due to the nature of the chemistry of calcining, it emitssignificant amounts of CO₂ not only due to its thermal energy demands(which are generally powered by the burning of coal), but also or mostlydue to the CO₂ directly released from the decomposition of CaCO₃ intoCaO and CO₂. The resulting calcium chloride byproduct is also generallya waste product, usually disposed by discarding into the ocean.

Summary of Example Embodiments

Some of the example embodiments may comprise a process for producingsodium bicarbonate or sodium carbonate, which may be net CO₂ negative(both for producing sodium bicarbonate and/or sodium carbonate), may notcalcine calcium carbonate, produces HCl byproduct, may not require anelectrolyzer, and/or may be more profitable than the Solvay Process.Example Embodiment 3, for example, may:

-   -   Net convert/sequester 304% more CO₂ during the production of        sodium bicarbonate than the Solvay process (0.834 moles CO₂ per        mole sodium bicarbonate for Example Embodiment 1 vs. 0.274 moles        CO₂ per mole sodium bicarbonate for the Solvay process)    -   Net convert/sequester 0.334 moles CO₂ per mole of sodium        carbonate produced in the production of sodium carbonate (Solvay        process net emits 0.226 moles of CO₂ per mole of sodium        carbonate produced [Solvay process net pollutes/emits CO₂ during        the production of sodium carbonate, does not        sequester/convert]).    -   Provide 24.8-42.9% more net profit per ton of Sodium Bicarbonate        produced than the Solvay process

Calculations for the above CO₂ and cost values may be shown in tablesherein.

Example Embodiment 3

-   1) NaCl(aq)+NH₃(g or aq)+CO₂(g or aq)+H₂O    NaHCO₃(s)+NH₄Cl(aq)-   2) At a temperature near or below 10° C., NaCl may possess a greater    solubility in water than NH₄Cl. Due to, for example, the common-ion    effect, adding NaCl to the solution produced in reaction 1 (which    may be after NaHCO₃(s) separation) at a solution temperature near or    below 10° C. may result in the dissolution of NaCl and the    precipitation of at least a portion of the NH₄Cl(s). The    precipitated NH₄Cl(s) may be transferred to reaction 3 and the    remaining NaCl(aq) solution after NH₄Cl(s) precipitate separation    may be transferred to reaction 1.-   3) NH₄Cl(s)+½ ZnO(s)    NH₃(g)+½ ZnCl₂(s)+½ H₂O(g) (+116.33 kJ/mol of NH₃; 210° C.)-   4) ½ ZnCl₂(s)+½ H₂SO₄(aq)    ½ ZnSO₄(s)+HCl(aq) (−41.5 kJ/mol of NH₃)-   5) ½ ZnSO₄(s)    ½ ZnO(s)+½ SO₃(g) (+117.57 kJ/mol of NH₃; 920-980° C.)    -   Note: ½ ZnSO₄(s)        ½ ZnO(s)+½ SO₂(g)+¼O₂ (g) (Alternative Reaction; if desired O₂        may be reacted with SO₂ to produce SO₃ before reaction ‘(6)’        using, if desired, a catalyst)-   6) ½ SO₃(g)+½ H₂O (l)    ½ H₂SO₄(1) (−85 kJ/mol of NH₃, can be utilized to produce steam or    heat produced may supplement heat requirements of reaction ‘(3)’,    although this heat recovery not required and, for purposes of being    conservative, the heat recovery is not included in energy    consumption calculations)

Inputs Outputs NaCl NaHCO₃ CO₂ HCl Heat HCl(aq) H₂O

Reaction 1 Further Description and Proof:

Reaction 1 may comprise the first reaction of the Solvay process and theHou Debang modified Solvay process.

Reaction 2 Further Description and Proof:

Reaction 2 may employ the Hou Debang process method for precipitation ofNH₄Cl.

Reaction 3 Further Description and Proof:

Reaction 3 may involve reacting ammonium chloride and zinc oxide at arelatively elevated temperature to form zinc chloride, water vapor, andammonia gas. The reaction may involve decomposing ammonium chloride andpassing the gas mixture over heated or unheated zinc oxide. The reactionmay involve heating a mixture of ammonium chloride and zinc oxide andforming zinc chloride and ammonia according to Reaction 3. It may bepreferred to react a mixture of ammonium chloride and zinc oxide becausethe solid mixture has been shown to produce reaction products with lowertemperature requirement (210° C. for mixture vs. 338° C. for ammoniumchloride alone) and lower heat input requirement (+116.33 kJ/mol NH₃ formixture vs. +228.55 kJ/mole NH₃ for ammonium chloride alone). Thereaction shown in reaction 3 has been demonstrated in literature in thearticle ‘Reaction of Zinc Chloride with Zinc Oxide’ by Borisov et al.Borisov et al found the reactants initially form ammonium chlorozincates((NH₄)₃ZnCl₄) at 150° C., with the evolution of NH₃(g) and H₂O(g).Borisov et al found the mixture of ammonium chloride and zinc oxidecompletely converts into products shown in reaction 3 at about 210° C.Borisov et al found a stoichiometric amount of NH₃ formed and thepresence of zinc did not cause the NH₃ to decompose.

It is important to note that zinc oxide may be recycled internally fromReaction 3.

It is important to note metals other than or in addition to zinc may beemployed, which may include, but are not limited to, one or more or acombination of the following: iron, lead, copper, cobalt, nickel,manganese, chromium, silver, scandium, vanadium, titanium, aluminum,magnesium, calcium, sodium, potassium, Yttrium, Zirconium, Niobium,Molybdenum Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium,Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold,Mercury, Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium,Meitnerium, Ununnilium, Unununium, or Ununbium.

Reaction 4 Further Description and Proof:

Reaction 4 involves reacting zinc chloride with sulfuric acid form zincsulfate and hydrochloric acid. The enthalpy of Reaction 4 may bestrongly exothermic and favorable and sulfuric acid may be a strongeracid than hydrochloric acid. Reaction 4 may require cooling. Saidcooling may involve recovering heat. Recovered heat may be employed tofacilitate removal or distillation of excess water or separate residualzinc sulfate or zinc chloride from hydrochloric acid. Depending on theconcentration of sulfuric acid, zinc chloride may be placed insufficient water to ensure there is enough water for the producthydrochloric acid to fully dissolve and form hydrochloric acid, ashydrochloric acid may require stoichiometrically more water thansulfuric acid to remain in solution. Alternatively, or additionally, aportion of hydrochloric acid may form as a gas, and may be condensed orrecovered or converted into an aqueous solution or a combinationthereof. Zinc chloride or zinc sulfate may be present primarily at thesolid phase due to, for example, limited amount of relative water and/orthe salting-out effects of HCl or H₂SO₄ in solution. Residual zincchloride or zinc sulfate may comprise a membrane-based process, a solidmembrane, distillation, electrodialysis, ion exchange, crystallization,cryodesalination, freezing desalination, cooling precipitation,precipitation, ‘salting-out’, common-ion effect, or a combinationthereof.

Reaction 5 Further Description and Proof:

Reaction 5 involves decomposing zinc sulfate into zinc oxide and sulfurtrioxide or sulfur dioxide and O₂ or both. According to ‘Kinetics of theThermal Decomposition of Zinc Sulfate’ by Ibanez et al, zinc sulfatedecomposes into zinc oxide and sulfur trioxide or sulfur dioxide or O₂or a combination thereof starting at about 920° C. Zinc oxide may betransferred or employed or both to Reaction 3 and sulfur trioxide orsulfur dioxide or O₂ or a combination thereof may be employed inReaction 6.

Reaction 6 Further Description and Proof:

Reaction 6 may involve the formation of sulfuric acid from sulfurtrioxide or sulfur oxides which may be converted into sulfur trioxide orsulfuric acid. Reaction 6 is well known in industry to produce sulfuricacid and may be conducted using one or more or a combination of methodsfor producing sulfuric acid in the art. Reaction 6 is highly exothermicand heat from the reaction may be recovered as, for example, steam. Itmay be possible to employ heat from Reaction 6 to power a portion of thethermal duty of Reaction 1. Sulfuric acid product may be employed inReaction 4.

Comparison of Example Embodiment 3 to Process Involving RecoveringAmmonia with Calcium Oxide—Energy Balance, CO₂ Emissions Balance, andValue of Byproducts

Energy Consumption:

Comparison of Heat Input Requirements between Process for RegeneratingNH₃ from NH₄Cl with CaO Example Embodiment 3 ½ CaCO₃ 

 ½ CaO + ½ CO₂ Reaction 3: (+89 kJ/mol NH₃; 825° C.) NH₄C1(s) + ½ZnO(s) 

 NH₃(g) + ½ ZnCl₂(s) + ½ H₂O(g) (+116.33 kJ/ mol of NH₃; 210° C.)Reaction 5: ½ ZnSO₄(s) 

 ½ ZnO(s) + ½ SO₃(g) (+117.57 kJ/mol of NH₃; 920-980° C.) Total: 89kJ/mol NH₃ Total without Heat Recovery from Reaction 6: 233 kJ/mol NH₃Total with Heat Recovery from Reaction 6: 148 kJ/mol NH₃ Note: Usingrecovered heat may be possible because of the relatively low requiredtemperature of Reaction 3.

Steam Quality Heat Production - Sufficiently High Temperature Heat forUseful Steam Production Comparison Process for Regenerating NH₃ fromNH₄Cl with CaO Example Embodiment 3 ½ CaO + ½ H₂O 

 ½ Ca(OH)₂ Reaction 6: (−31.85 kJ/mol of NH₃) ½ SO₃(g) + ½ H₂O(l) 

 ½ H₂SO₄(l) (−85 kJ/mol of NH₃ Total: −31.85 kJ/mol NH₃ (although Total:−85 kJ/mole NH₃ heat is not usable for calcination Note: Using recoveredheat may be as it is significantly lower possible because of therelatively temperature) low required temperature of Reaction 3.

CO₂ Emissions:

Note: CO₂ emissions savings/net CO₂ sequestration is not due to fuelswitching.

CO₂ Emissions Production Comparison (Note: Both Processes Consume theSame About of CO₂ in their Products, so Focus of Table is on Reactants)Process for Regenerating NH₃ from NH₄Cl with CaO Example Embodiment 3Calcination Non-Heat Emissions: Heat Emissions using Natural Gas ½CaCO₃ 

 ½ CaO + ½ CO₂ without Heat Recovery from (½ mole of CO₂ per mole NH₃)Reaction 6: Calcination Heat Emissions: 0.261 CH₄ + 0.261 O₂ 

 0.261 0.226 C + 0.226 O₂ 

 0.226 CO₂ + 0.261 H₂O (−233 kJ heat; CO₂ (−89 kJ heat; 0.226 moles0.261 mole of CO₂ per mole NH₃) of CO₂ per mole NH₃) Heat Emissionsusing Natural Gas with Heat Recovery from Reaction 6: 0.166 CH₄ + 0.166O₂ 

 0.166 CO₂ + 0.166 H₂O (−148 kJ heat; 0.166 mole of CO₂ per mole NH₃)Total: 0.726 mole CO₂ per Total without Heat Recovery from mole NH₃Reaction 6: 0.261 mole CO₂ per mole NH₃ (64% less CO₂ emissions thanSolvay Process) Total with Heat Recovery from Reaction 6: 0.166 mole CO₂per mole NH₃ (77% less CO₂ emissions than Solvay Process)

Net CO₂ Emissions Comparison (Production of Sodium Bicarbonate) Processfor Regenerating NH₃ Type from NH₄Cl with CaO Example Embodiment 3 CO₂Calcination Non-Heat Emissions: Heat Emissions using Natural Gas orEmissions ½ CaCO₃ 

 ½ CaO + ½ CO₂ (½ Flare Gas without Heat Recovery Production mole of CO₂per mole NH₃) from Reaction 6: Calcination Heat Emissions: 0.261 CH₄ +0.261 O₂ 

 0.261 CO₂ + 0.226 C + 0.226 O₂ 

 0.226 CO₂ (−89 0.261 H₂O (−233 kJ heat; 0.261 mole of kJ heat; 0.226moles of CO₂ per mole CO₂ per mole NH₃) NH₃) Total: 0.261 mole of CO₂per mole Total: 0.726 mole CO₂ per mole NH₃ NH₃ Or: Heat Emissions usingNatural Gas or Flare Gas with Heat Recovery from Reaction 6: 0.166 CH₄ +0.166 O₂ 

 0.166 CO₂ + 0.166 H₂O (−148 kJ heat; 0.166 mole of CO2 per mole NH₃)Total: 0.166 mole of CO₂ per mole NH₃ CO₂ NaCl(aq) + NH₃(g or aq) +CO₂(g or NaCl(aq) + NH₃(g or aq) + CO₂(g or Emissions aq) + H₂O 

 NaHCO₃(s) + aq) + H₂O 

 NaHCO₃(s) + Consumption NH₄Cl(aq) NH₄Cl(aq) Total: 1 mole CO₂ per moleNH₃ Total: 1 mole CO₂ per mole NH₃ Total Net CO₂ (0.726 mole CO₂produced) − (1 mole (0.261 mole CO₂ produced) − (1 mole (End-to-End CO₂consumed) = −0.274 moles CO₂ CO₂ consumed) = −0.739 moles CO₂ Emissionsor Total: Net sequesters 0.274 mole Total: Net sequesters 0.739 moleSequestration) CO₂ per mole NH₃ internally recycled CO₂ per mole NH₃internally recycled or per mole Sodium or per mole Sodium (270% more CO₂sequestered than Solvay Process) Or: (0.166 mole CO₂ produced) − (1 moleCO₂ consumed) = −0.834 moles CO₂ Total: Net sequesters 0.834 mole CO₂per mole NH₃ internally recycled or per mole Sodium (304% more thanSolvay Process)

Net CO₂ Emissions Comparison (Production of Sodium Carbonate) Processfor Regenerating NH₃ from Type NH₄Cl with CaO Example Embodiment 3 CO₂Calcination Non-Heat Emissions: Heat Emissions using Natural Gas orEmissions ½ CaCO₃ 

 ½ CaO + ½ CO₂ (½ mole Flare Gas without Heat Recovery Production of CO₂per mole NH₃) from Reaction 6: Calcination Heat Emissions: 0.261 CH₄ +0.261 O₂ 

 0.261 CO₂ + 0.226 C + 0.226 O₂ 

 0.226 CO₂ (−89 0.261 H₂O (−233 kJ heat; 0.261 mole of kJ heat; 0.226moles of CO₂ per mole CO₂ per mole NH₃) NH₃) Decomposition of SodiumDecomposition of Sodium Bicarbonate to Sodium Carbonate: Bicarbonate toSodium Carbonate: NaHCO₃ 

 ½ Na₂CO₃ + ½ CO₂ + ½ NaHCO₃ 

 ½ Na₂CO₃ + ½ CO₂ + ½ H₂O H₂O Total: 0.761 mole of CO₂ per mole Total:1.226 mole CO₂ per mole NH₃ NH₃ Or: Heat Emissions using Natural Gas orFlare Gas with Heat Recovery from Reaction 6: 0.166 CH₄ + 0.166 O₂ 

 0.166 CO₂ + 0.166 H₂O (−148 kJ heat; 0.166 mole of CO₂ per mole NH₃)Total: 0.666 mole of CO₂ per mole NH₃ CO₂ NaCl(aq) + NH₃(g or aq) +CO₂(g or NaCl(aq) + NH₃(g or aq) + CO₂(g or Emissions aq) + H₂O 

 NaHCO₃(s) + aq) + H₂O 

 NaHCO₃(s) + Consumption NH₄Cl(aq) NH₄Cl(aq) Total: 1 mole CO₂ per moleNH₃ Total: 1 mole CO₂ per mole NH₃ Total Net CO₂ (1.226 mole CO₂produced) − (1 mole (0.761 mole CO₂ produced) − (1 mole (End-to-End CO₂consumed) = 0.226 moles CO₂ CO₂ consumed) = −0.239 moles CO₂ Emissionsor Total: Net emits 0.226 mole CO₂ per Total: Net sequesters 0.239 moleSequestration) mole NH₃ internally recycled or per CO₂ per mole NH₃internally recycled mole Sodium or per mole Sodium (Substantially netsequesters CO₂, while Solvay process net emits CO₂) Or: (0.666 mole CO₂produced) − (1 mole CO₂ consumed) = −0.334 moles CO₂ Total: Netsequesters 0.334 mole CO₂ per mole NH₃ internally recycled or per moleSodium (Substantially net sequesters CO₂, while Solvay process net emitsCO₂)

Value of Byproducts (Table):

Value of Byproducts (Sodium Bicarbonate) Process for Regenerating NH₃from NH₄Cl with CaO Example Embodiment 3 Inputs Sodium Chloride: 1metric ton Sodium Chloride: 1 metric ton required; required; $40 permetric ton; $40 total $40 per metric ton; $40 total CO₂: Assumed to comefrom flue gas CO₂: Assumed to come from flue gas or or other low valuesource other low value source Calcium Carbonate: 0.85632 metric NaturalGas: 0.072326 metric ton ton required; $50 per metric ton; required;$115.88 per metric ton ($2.17 $42.816 total per MMBtu); $8.38 totalCoal: 0.046443 metric ton required; Water: 0.3089 metric ton required;$0.30 $48.05 per metric ton; $2.232 total per metric ton; $0.093 totalWater: 0.3089 metric ton required; Total Input Cost: $48.47 $0.30 permetric ton; $0.093 total Note: Natural Gas Heat Requirement Total InputCost: $85.141 Assumes No Heat Recovery from Reaction 6 in Embodiment 1for a conservative estimate. Outputs Sodium Bicarbonate: 1.43749 metricSodium Bicarbonate: 1.43749 metric ton ton produced; $250 per metricton; produced; $250 per metric ton; $359.37 $359.37 total total CalciumChloride: 0.94952 metric ton Hydrochloric Acid: 0.62389 metric tonproduced; $42 per metric ton; $39.88 produced; $130 per metric ton;$81.10 total total Total Output Value: $399.25 Total Output Value:$440.47 Note: Calcium chloride is typically a waste product and notsold. The commodity Calcium Chloride price for deicing roads is used,although this may be assigning too much value to Calcium Chloride. NetValue Total Net Value per Ton of NaCl: Total Net Value per Ton of NaCl:$314.11 $392.00 (24.8% more OPEX profit than Solvay Process)

Example Exemplary Embodiments

-   1. A process for producing separated ammonia and hydrochloric acid    from ammonium chloride comprising:    -   Reacting ammonium chloride with zinc oxide, forming zinc        chloride, gaseous ammonia, and gaseous water vapor    -   Reacting zinc chloride with sulfuric acid, forming zinc sulfate        and hydrochloric acid Thermally decomposing zinc sulfate to        produce zinc oxide-   2. The process of embodiment 1 wherein the thermal decomposing of    zinc sulfate produces zinc oxide, sulfur dioxide, diatomic oxygen,    or sulfur trioxide, or a combination thereof-   3. The process of embodiment 2 wherein the sulfur dioxide is further    reacted with diatomic oxygen to produce sulfur trioxide-   4. The process of embodiment 2 wherein said sulfur dioxide, diatomic    oxygen, or sulfur trioxide, or a combination thereof are reacted    with water to form sulfuric acid-   5. The process of embodiment 4 wherein said formed sulfuric acid is    reacted with zinc chloride in the process-   6. The process of embodiment 1 wherein gaseous water vapor is    condensed-   7. The process of embodiment 1 wherein gaseous ammonia and gaseous    water vapor are condensed-   8. The process of embodiment 1 wherein at least a portion of zinc    chloride, zinc sulfate, or both are at a solid phase-   9. The process of embodiment 1 wherein at least a portion of    sulfuric acid, hydrochloric acid, or both are at a liquid phase-   10. The process of embodiment 1 wherein at least a portion of solid    zinc sulfate is separated from at least a portion liquid    hydrochloric acid-   11. The process of embodiment 1 wherein residual dissolved zinc    sulfate, or residual dissolved zinc chloride, or a combination    thereof are separated from hydrochloric acid-   12. The process of embodiment 11 wherein said separating comprises a    membrane based process, a solid membrane, distillation,    electrodialysis, ion exchange, crystallization, precipitation,    ‘salting-out’, common-ion effect, or a combination thereof-   13. The process of embodiment 1 wherein said reacting ammonium    chloride with zinc oxide comprises heating a mixture of solid    ammonium chloride and solid zinc oxide to a temperature greater than    200° C.-   14. The process of embodiment 1 wherein said reacting ammonium    chloride with zinc oxide comprises heating a mixture of solid    ammonium chloride and solid zinc oxide to a temperature greater than    250° C.-   15. The process of embodiment 1 wherein said reacting ammonium    chloride with zinc oxide comprises contacting a gaseous mixture of    ammonia and hydrochloric acid with zinc oxide at a temperature    greater than 200° C.-   16. The process of embodiment 1 wherein said reacting ammonium    chloride with zinc oxide comprises contacting a gaseous mixture of    ammonia and hydrochloric acid with zinc oxide at a temperature    greater than or equal to 338° C.-   17. The process of embodiment 1 wherein said reacting ammonium    chloride with zinc oxide is conducted in a low diatomic oxygen    environment-   18. The process of embodiment 17 wherein low oxygen comprises a    diatomic oxygen concentration less than 1 percent by volume-   19. The process of embodiment 1 wherein the ammonium chloride is    sourced from a process for producing sodium bicarbonate or sodium    carbonate-   20. The process of embodiment 1 wherein the ammonia, water, or a    combination thereof is returned to a process for producing sodium    bicarbonate or sodium carbonate-   21. A process for producing sodium bicarbonate or sodium carbonate    from sodium chloride comprising:    -   Reacting sodium chloride with ammonia, carbon dioxide, and water        to form sodium bicarbonate and ammonium chloride    -   Reacting ammonium chloride with zinc oxide, forming zinc        chloride, gaseous ammonia, and gaseous water vapor    -   Reacting zinc chloride with sulfuric acid, forming zinc sulfate        and hydrochloric acid Decomposing zinc sulfate to produce zinc        oxide-   22. The process of embodiment 21 wherein decomposing zinc sulfate    further comprises forming sulfur dioxide, or diatomic oxygen, or    sulfur trioxide, or a combination thereof-   23. The process of embodiment 22 wherein said sulfur dioxide, or    diatomic oxygen, or sulfur trioxide, or a combination thereof are    reacted with water to produce sulfuric acid-   24. The process of embodiment 23 wherein said sulfuric acid is    employed in a reacting step of-   25. The process of embodiment 21 wherein said sodium bicarbonate is    decomposed into sodium carbonate or sodium sesquicarbonate and    carbon dioxide-   26. The process of embodiment 25 wherein at least a portion of said    carbon dioxide is employed in a reacting step of embodiment 21-   27. The process of embodiment 21 wherein said gaseous ammonia,    gaseous water vapor, or both are recirculated to or employed in a    preceding reacting step in embodiment 21-   28. The process of embodiment 21 wherein said sodium bicarbonate is    dissolved in the ocean for carbon sequestration, or reef    restoration, or coral restoration, or a combination thereof-   29. The process of embodiment 25 wherein said sodium carbonate or    sodium sesquicarbonate is dissolved in the ocean for carbon    sequestration, or reef restoration, or coral restoration, or    increasing dissolved carbonate ion concentration, or a combination    thereof-   30. The process of embodiment 21 wherein said carbon dioxide    comprises carbon dioxide captured from one or more or a combination    of emissions sources

Calcium Oxide Production without Calcining Calcium Carbonate

Background: Calcium oxide is an essential component of cement andquicklime. It is produced in excess of 300 million tons per year for usein quicklime and produced in excess of 2 billion tons per year for usein the production of cement. Calcium oxide is currently produced usingthe highly CO₂ emitting and energy intensive process of calciningcalcium carbonate, which involves heating calcium carbonate to anelevated temperature and decomposing calcium carbonate into calciumoxide and carbon dioxide. Due to the nature of the chemistry ofcalcining calcium carbonate, it emits significant amounts of CO₂ notonly due to its thermal energy demands (which are generally powered bythe burning of coal), but also or mostly due to the CO₂ directlyreleased from the decomposition of CaCO₃ into CaO and CO₂. CalciningCaCO₃ comprises over 8% of global anthropogenic CO₂ emissions.

Summary of Example Embodiments: Example embodiments may involveproducing calcium oxide during the production of phosphoric acid fromcalcium phosphate. Example embodiments may enable the production ofcalcium oxide without the calcining of calcium carbonate and whileproducing valuable phosphoric acid.

Example Embodiment 1

-   1) Ca₃(PO₄)₂+6HNO₃+12H₂O    2H₃PO₄+3Ca(NO₃)₂+12H₂O-   2) 2H₃PO₄+3Ca(NO₃)₂+12H₂O    2H₃PO₄+3Ca(NO₃)₂.4H₂O(s) (may be cooled to near or below 0° C.    during or after reaction)-   3) 3Ca(NO₃)₂.4H₂O(s)    3CaO(s)+12H₂O(g)+6NO₂(g)+1.5O₂(g)-   4) 6NO₂(g)+1.5O₂(g)+3H₂O(l)    6HNO₃(l or aq)

Inputs Outputs Ca₃(PO₄)₂ 3CaO Heat 2 H₃PO₄ H₂O H₂O (although may not bechemically produced, there may be net production or absorption of H₂O)

Reaction 1 and 2 Further Description and Proof:

Reactions 1 and 2 may involve the first two reactions or steps of theOdda Process or the Nitrophosphate Process.

Reaction 3 Further Description and Proof:

Reaction 3 may involve the thermal decomposition of calcium nitrate orhydrates of calcium nitrate or both or a combination thereof. Accordingto a research paper on the thermal decomposition of calcium nitrate, ‘Akinetic and mechanistic study of the thermal decomposition of calciumnitrate’ by Ettarh et al, calcium nitrate melts and simultaneouslydecomposes in a temperature range around 562° C., proceeding to form thereaction products described in reaction 3.

The resulting calcium oxide may be employed for applications of calciumoxide and may comprise a valuable byproduct. The nitrogen oxides andoxygen produced may be employed, for example, in reaction 4 to producenitric acid, which may be recycled internally.

Reaction 4 Further Description and Proof:

Reaction 4 may involve forming nitric acid from nitrogen oxides, oxygen,and water. The nitrogen oxides and oxygen may form internally (forexample: reaction 3) and the resulting nitric acid may be recycled orused internally (for example: reaction 1). The process for nitric acidproduction may be simplified in reaction 4. For example, nitrogenmonoxide is often produced and must be oxidized to nitrogen dioxide andre-introduced to water. The steps involved with producing nitric acidfrom nitric oxides may follow steps and procedures known in the art fornitric acid production, such as the steps and procedures performed bythe Ostwald Process. The production of nitric acid from nitrogen oxidesand water may be highly exothermic and heat may be recovered from saidreaction and utilized internally or externally in other processes orboth.

Further Notes:

Note: Any excess water may be removed from system. Similarly, water maybe added to the system if desired. Water removal may be conducted by forexample, including, but not limited to, one or more or a combination ofthe following: forward osmosis, decanter, separatory funnel, coalescer,centrifuge, filter, switchable solvent, cyclone, semi-permeablemembrane, nanofiltration, organic solvent nanofiltration, reverseosmosis, ultrafiltration, microfiltration, hot nanofiltration, hotultrafiltration, distillation, membrane distillation, flashdistillation, multi-effect distillation, mechanical vapor compressiondistillation, or hybrid systems.

Note: Sodium Bicarbonate may be decomposed to form Sodium Carbonate,Sodium hydroxide, Sodium Sesquicarbonate, or a combination thereof, orother sodium—carbon dioxide or sodium bicarbonate derivative chemicals.

Note: Separation Devices may include, but are not limited to, one ormore or a combination of the following: decanter, separatory funnel,coalescer, centrifuge, filter, switchable solvent, cyclone,semi-permeable membrane, nanofiltration, organic solvent nanofiltration,reverse osmosis, ultrafiltration, microfiltration, hot nanofiltration,hot ultrafiltration, distillation, membrane distillation, flashdistillation, multi-effect distillation, mechanical vapor compressiondistillation, or hybrid systems

Note: The temperature of recovered heat may be increased using a heatpump or a refrigeration cycle, if, for example, higher temperature heatis required for one or more process steps or one or more applications.For example, if recovered heat is in the form of steam, said steam maybe compressed to a greater pressure, which may enable said steam tocondense at a higher temperature and/or supply higher temperature heat.

Note: Heat sources may include, but are not limited to, one or more or acombination of the following: flare gas heat, natural gas combustion,nuclear heat, Waste Heat, Ambient Temperature Changes, DiurnalTemperature Variation, Thermocline liquid body, thermocline solid body,thermocline gaseous body, Thermocline of a water body, halocline, heatpump, solar thermal, solar thermal pond, light, electricity, steam,combustion, compression, pressure increase, geothermal, radiative heat,condensation, exothermic dissolution, exothermic precipitation,exothermic formation of more liquid phases, exothermic formation of lessliquid phases, exothermic phase change, or other heat sources describedherein.

Note: Systems and methods described herein may be batch, semi-batch, orcontinuous, or a combination thereof.

Note: Metals other than or in addition to zinc may be employed, whichmay include, but are not limited to, one or more or a combination of thefollowing: iron, lead, copper, cobalt, nickel, manganese, chromium,silver, scandium, vanadium, titanium, aluminum, magnesium, calcium,sodium, potassium, Yttrium, Zirconium, Niobium, Molybdenum Technetium,Ruthenium, Rhodium, Palladium, Silver, Cadmium, Hafnium, Tantalum,Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, Mercury,Rutherfordium, Dubnium, Seaborgium, Bohrium, Hassium, Meitnerium,Ununnilium, Unununium, or Ununbium.

Note: Reactions or systems and methods, steps, or a combination thereofherein may comprise a batch, semi-batch, semi-continuous, continuousstirred reactor (CSTR), continuous, or a combination thereof.

Note: The dissolution of calcium chloride in one or more embodiments maypre-heat or provide supplemental heating to an ammonium chloride—leanaqueous solution. Said dissolution and/or resulting pre-heating mayoccur before a solution comprising calcium chloride and ammoniumchloride is reacted with ammonium sulfate. Calcium chloride dissolutionis generally exothermic and said exothermic dissolution may provide atleast a portion of the heat required to ensure the solution is at asufficiently high temperature before reaction with ammonium sulfate. Asufficiently high temperature may be beneficial, as a greatertemperature may enable greater solubility of ammonium chloride and/orammonium sulfate during the reaction. A sufficiently high temperaturemay enable ammonium chloride to remain dissolved during the reactionbetween calcium chloride and ammonium sulfate, which may enable theformation of a precipitate comprising mostly or entirely calciumsulfate. A sufficiently high temperature may enable ammonium chloride toremain dissolved during the reaction between calcium chloride andammonium sulfate (which forms additional ammonium chloride as aproduct), which may enable the formation of a precipitate comprisingmostly or entirely calcium sulfate. After separation of calcium sulfateprecipitate, the remaining solution may be rich in ammonium chloride(aq)and may be cooled to precipitate a portion of ammonium chloride(s).After the ammonium chloride precipitate is separated, the remainingsolution may comprise ammonium chloride—lean aqueous solution and may beemployed to the first step.

Note: Depending on the operating conditions, phases of inputs,concentrations, or a combination thereof, heating or cooling or both maybe required in one or more or a combination of the steps or parts of oneor more or a combination of embodiments.

Note: The present invention may employ other carbonate or bicarbonatesalts as feedstocks, which may include, but are not limited to, sodiumand potassium carbonates or bicarbonates.

Note: May employ materials compatible with one or more or a combinationof the following: SO2, CO₂, or H₂O or one or more of the fuels (if any)employed in heating and/or their combustion products. It may bedesirable for said materials to be compatible at temperature rangeswhich the materials will be operating

Note: Advantageous, the present invention does not require an airseparation unit or post-combustion CO₂ capture to produce pure CO₂. Alsoadvantageously, pure CO₂ may be produced at a high pressure and/orrelatively low temperature and/or with relatively low water vaporconcentration.

Note: It may be desirable for the CaCO3 or SO2 or CaSO3 or CaO or acombination thereof in an oxygen-free or very low oxygen environment. Anoxygen-free or very low oxygen environment may, for example, prevent theoxidation of SO2 or CaSO3 or other SO3 salt into a SO4 salt.

Note: The present invention may be employed to regenerate CaO from CaCO3or similar carbonate or bicarbonate molecules in a CO₂ capture process.For example, the present invention may be employed in a device tocapture CO₂ from the air.

Note: The SO2 may be substituted with nitric acid (HNO3). Ca(NO3)2(which may be a resulting byproduct) can be thermally decomposed in asimilar manner to CaSO3 to form CaO and NOx or O2 or NO2 or NO or acombination thereof. NOx, NO2, or NO may be converted back into nitricacid through reaction with water in, for example, the NOx+O2 and NOx+H₂Oreaction steps of the Ostwald process, regenerating the nitric acid inthe present embodiment. Advantageously, Ca(NO3)2 does not oxidize in thepresence of O2, which may enable the process to operate in anenvironment with the presence of O2, if desired.

Note: The carrier gas may comprise a reactive gas if desired. Forexample, steam may be employed as a carrier gas. Advantageously, steammay condense following calcination and the heat generated may berecoverable and the heat generated may exceed initial heat input togenerate steam due to, for example, the exothermic dissolution of SO₂ inthe condensed steam (water) and/or the exothermic reaction of H₂O withCaO to produce calcium hydroxide. It is important to note that calciumhydroxide may be a byproduct of this version of the present invention.

Note: Any excess water may be removed from system. Similarly, water maybe added to the system if desired. Water removal may be conducted by forexample, including, but not limited to, one or more or a combination ofthe following: forward osmosis, decanter, separatory funnel, coalescer,centrifuge, filter, switchable solvent, cyclone, semi-permeablemembrane, nanofiltration, organic solvent nanofiltration, reverseosmosis, ultrafiltration, microfiltration, hot nanofiltration, hotultrafiltration, distillation, membrane distillation, flashdistillation, multi-effect distillation, mechanical vapor compressiondistillation, or hybrid systems.

Note: Sodium salts may be employed. Sodium Bicarbonate may be decomposedto form Sodium Carbonate, Sodium hydroxide, Sodium Sesquicarbonate, or acombination thereof, or other sodium—carbon dioxide or sodiumbicarbonate derivative chemicals.

Note: Separation Devices may include, but are not limited to, one ormore or a combination of the following: decanter, separatory funnel,coalescer, centrifuge, filter, switchable solvent, cyclone,semi-permeable membrane, nanofiltration, organic solvent nanofiltration,reverse osmosis, ultrafiltration, microfiltration, hot nanofiltration,hot ultrafiltration, distillation, membrane distillation, flashdistillation, multi-effect distillation, mechanical vapor compressiondistillation, or hybrid systems

Note: Heat sources may include, but are not limited to, one or more or acombination of the following: flare gas heat, natural gas combustion,nuclear heat, Waste Heat, Ambient Temperature Changes, DiurnalTemperature Variation, Thermocline liquid body, thermocline solid body,thermocline gaseous body, Thermocline of a water body, halocline, heatpump, solar thermal, solar thermal pond, light, electricity, steam,combustion, compression, pressure increase, geothermal, radiative heat,condensation, exothermic dissolution, exothermic precipitation,exothermic formation of more liquid phases, exothermic formation of lessliquid phases, exothermic phase change, or other heat sources describedherein.

Note: Systems and methods described herein may be batch, semi-batch, orcontinuous, or a combination thereof.

Note: Sodium bicarbonate may be thermally decomposed into at least aportion carbon dioxide to, for example, produce sodium carbonate orsodium sesquicarbonate. Said carbon dioxide may be recycled internally,for example, to a carbon dioxide absorption step. Said carbon dioxide,may improve absorption characteristics including, but not limited to,one or more or a combination of the following: absorption rate, maximumcarbon dioxide loading, absorption capacity, solution carrying capacity,sodium bicarbonate recovery yield, sodium bicarbonate recovery rate, orsodium bicarbonate recovery rate per a unit volume or mass of solution.Said carbon dioxide may increase the concentration of carbon dioxide inone or more or a combination of parts of the system, for example, whichmay be related, including, but not limited to, one or more or acombination of the following: carbon dioxide solutions, carbon dioxidegases, carbon dioxide absorption, bicarbonate salts, salts.

Note: Solutions may be passed or cycled or recycled or recirculatedthrough a step more than once. Said ‘passed or cycled or recycled orrecirculated’ may be conducted before, for example, proceeding to a nextstep. Said solutions may comprise, for example, absorption solutions orsolutions undergoing precipitation.

Note: Magnesium chloride may be an input in the system. For example,magnesium chloride may be employed in addition to or instead of calciumchloride in one or more or a combination of the embodiments.

Note: One or more or a combination of the embodiments described hereinmay be employed as a net carbon dioxide emission negative method forpermanently or semi-permanently sequestering carbon dioxide. Forexample, the sodium bicarbonate, or sodium sesquicarbonate, or sodiumcarbonate or a combination thereof produced by one or more embodimentsmay be dissolved in the ocean. Adding net carbon dioxide emissionnegative sodium bicarbonate, or sodium sesquicarbonate, or sodiumcarbonate or a combination thereof to the ocean may have multiplebenefits, which may include, but are not limited to, one or more or acombination of the following: permanent or semi-permanent sequestrationof carbon dioxide in the ocean; increasing the pH of ocean water;increasing the concentration of carbonate ions in the ocean; bufferingocean acidification, restoring coral reefs; restoring marine life; localrejuvenation of marine life; local rejuvenation of coral; rejuvenationof coral.

Note: To ensure full mixing of ammonium chloride and zinc oxide, aqueousammonium chloride may be mixed with finely ground or dispersed solidzinc oxide. Water may be evaporated or distilled from said aqueousammonium chloride while said aqueous ammonium chloride is in contactwith said zinc oxide, which may result in the formation of a relativelyevenly distributed mixture of ammonium chloride and zinc oxide.

Note: ‘Chloride’ may be provides as an example anion. Other anions maybe employed. For example, other halogens may be employed in addition toor instead of chloride or chlorine, which may include, but are notlimited to, one or more or a combination of the following: fluoride orfluorine, bromide or bromine, or iodide or iodine.

Note: Cooling and/or heating may be conducted at addition or differenttemperatures and/or at additional or different locations than describedherein.

Note: Any excess water may be removed from system. Similarly, water maybe added to the system if desired. Water removal may be conducted by forexample, including, but not limited to, one or more or a combination ofthe following: forward osmosis, decanter, separatory funnel, coalescer,centrifuge, filter, switchable solvent, cyclone, semi-permeablemembrane, nanofiltration, organic solvent nanofiltration, reverseosmosis, ultrafiltration, microfiltration, hot nanofiltration, hotultrafiltration, distillation, membrane distillation, flashdistillation, multi-effect distillation, mechanical vapor compressiondistillation, or hybrid systems.

Note: Sodium salts may be employed. Sodium Bicarbonate may be decomposedto form Sodium Carbonate, Sodium hydroxide, Sodium Sesquicarbonate, or acombination thereof, or other sodium—carbon dioxide or sodiumbicarbonate derivative chemicals.

Note: Separation Devices may include, but are not limited to, one ormore or a combination of the following: decanter, separatory funnel,coalescer, centrifuge, filter, switchable solvent, cyclone,semi-permeable membrane, nanofiltration, organic solvent nanofiltration,reverse osmosis, ultrafiltration, microfiltration, hot nanofiltration,hot ultrafiltration, distillation, membrane distillation, flashdistillation, multi-effect distillation, mechanical vapor compressiondistillation, or hybrid systems, freezing desalination, cryodesalination

Note: Heat sources may include, but are not limited to, one or more or acombination of the following: flare gas heat, natural gas combustion,nuclear heat, Waste Heat, Ambient Temperature Changes, DiurnalTemperature Variation, Thermocline liquid body, thermocline solid body,thermocline gaseous body, Thermocline of a water body, halocline, heatpump, solar thermal, solar thermal pond, light, electricity, steam,combustion, compression, pressure increase, geothermal, radiative heat,condensation, exothermic dissolution, exothermic precipitation,exothermic formation of more liquid phases, exothermic formation of lessliquid phases, exothermic phase change, or other heat sources describedherein.

Note: Systems and methods described herein may be batch, semi-batch, orcontinuous, or a combination thereof.

Note: One or more or a combination of embodiments of the presentinvention may comprise a retrofit to pre-existing processes forproducing sodium bicarbonate or sodium carbonate or other carbonate orbicarbonate salts. For example, some embodiments of the presentinvention may enable the production of ammonia from ammonium chloride,without the calcination of calcium carbonate or using calcium oxide. Forexample, some embodiments of the present invention may enable theproduction of ammonia and/or hydrochloric acid from ammonium chloride,which may provide greater value than an ammonium chloride byproduct.

Note: One or more or a combination of embodiments of the presentinvention may require solid handling or solid transfer or solid storage.Solid transfer may include, but is not limited to, conveyor belts, screwconveyors, bucket elevators, belt conveyors, pneumatic conveyors, or acombination thereof. Solid storage or transport or a combination thereofmay include, but is not limited to, bin, or silo, hopper cars, bulksacks, or other solids shipping containers, or a combination thereof.

Note: Temperatures in one or more parts of one or more embodiments mayinclude, but are not limited to, greater than, equal to, or less thanone or more or a combination of the following in degrees Celsius: −50,−40, −30, −20, −10, 0, 5, 10, 15, 20, 25, 30 35, 40, 45, 50, 55, 60, 65,70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180,190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320,330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460,470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600,610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740,750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880,890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, 1000, 1010, 1020,1030, 1040, 1050, 1060, 1070, 1080, 1090, 1100, 1150, 1200, 1250, 1300,1350, 1400, 1450, 1500, 1600, 1700, 1800, 1900, 2000, 2250, 2500, 2750,3000

Note: Sodium may be provided as an example alkali. Other alkali metalsalts or cations may be employed instead of or in addition to sodium.For example, potassium or lithium or rubidium or cesium or a combinationthereof may be employed.

Note: Ammonia may be provided as an example weak base. Other weak basesor weak base gases may be employed instead of or in addition to ammonia.For example, said other weak bases may include, but are not limited to,one or more or a combination of the following: amines, ammoniaderivatives, imines, azines, CO₂ capture absorbent cations, CO₂ captureabsorbents, or a combination thereof, or other weak bases, or other weakgases.

Note: CO₂ sources may include, but are not limited to, one or more or acombination of the following: Power Plant (Natural gas, coal, oil,petcoke, biofuel, municipal waste), Cement production, chemicalproduction, Waste Water Treatment, Landfill gas, Air, Metalproduction/refining (such as Iron, Steel, Aluminum, etc.), Glassproduction, Oil refineries, LNG liquification, HVAC, Transportationvehicles (ships, boats, cars, buses, trains, trucks, airplanes), NaturalGas, Biogas, Alcohol fermentation, Volcanic Activity, Decomposingleaves/biomass, Septic tank, Respiration, Manufacturing facilities,Fertilizer production, or Geothermal processes where CO₂(g) releasesfrom a well or wells.

Note: Input CO₂ vol % concentration may be greater than or equal to oneor more or a combination of the following volume percent concentrations:0%, or 0.001%, or 0.1%, or 0.5%, or 1%, or 1.5%, or 2%, or 2.5%, or 3%,or 3.5%, or 4%, or 4.5%, 5%, or 5.5%, or 6%, or 6.5%, or 7%, or 7.5%, or8%, or 8.5%, or 9%, or 9.5%, or 10%, or 10.5%, or 11%, or 11.5%, or 12%,or 12.5%, or 13%, or 13.5%, or 14%, or 14.5%, or 15%, or 20%, or 30%, or40%, or 50%, or 60%, or 70%, or 80%, or 90%, or 100%.

Note: A gas stream comprising CO₂ may be concentrated to a greaterconcentration of CO₂ or a greater partial pressure of CO₂ before beingabsorbed in one or more or a combination of embodiments of the presentinvention. Said concentrating may be conducted using including, but notlimited to, one or more or a combination of the following: gas membrane,or absorption/desorption CO₂ capture, or adsorption/desorption CO₂capture, or recirculated CO₂, or desorption CO₂, or CO₂ from one or moreor a combination of higher concentration CO₂ sources, or condensation ofnon-CO₂ gas, or cooling, or heating, or deposition, ordeposition/sublimination, or cryogenic separation, or compression, orpressurization, electrochemical process, or ion exchange, orelectrodialysis, or fuel cell, or a combination thereof.

Note: Absorption of a gas into a solution containing ammonia and/orabsorption of ammonia into a solution may result in the formation of aresidual or remaining gas stream comprising residual ammonia. Saidresidual or remaining gas stream may comprise, for example, remainingunabsorbed gases or inert gases. One or more or a combination ofembodiments herein may employ an ammonia recovery or ammonia abatementcycle or system. Alternately or additionally, ammonia may be removed toultra-low concentrations (e.g. single or double digit PPMconcentrations) using hydrochloric acid (which may be produced by someembodiments herein), and/or ammonia or hydrochloric acid or both may berecovered from the resulting ammonium chloride using one or more or acombination of embodiments herein.

Note: Ammonia losses may occur within one or more or a combination ofembodiments described herein. Makeup ammonia may be provided, forexample, as needed.

Note: In some embodiments, ammonia may form at elevated temperatures. Insome embodiments, if oxygen is present, some ammonia may undergocombustion. Ammonia combustion products, even at residual or lowconcentrations, may be present in one or more gases or liquids or solidsor a combination thereof in one or more or a combination of embodiments.Said ammonia combustion products may comprise, including, but notlimited to, nitrogen oxides, or nitrogen, or nitric acid, or aderivative thereof, or a combination thereof. Systems and methods fordetecting, treating, removing, economically using, recovering, or acombination thereof said ammonia combustion products may be employed.

Note: Filling, or reacting, or emptying, or a combination thereof may beconducted simultaneously if desired.

Additional Embodiments

-   1. A process comprising:

reacting ammonium chloride with zinc oxide to form a zinc chloride,ammonia, and water;

reacting the zinc chloride with sulfuric acid to form a zinc sulfate andhydrochloric acid; and

thermally decomposing the zinc sulfate to produce zinc oxide.

-   2. The process of embodiment 1 wherein the thermal decomposing of    zinc sulfate further produces sulfur dioxide, or diatomic oxygen, or    sulfur trioxide, or a combination thereof-   3. The process of embodiment 1 wherein the thermal decomposing of    zinc sulfate further produces sulfur dioxide and wherein the process    further comprises reacting sulfur dioxide with diatomic oxygen to    produce sulfur trioxide.-   4. The process of embodiment 2 which further comprises reacting said    sulfur dioxide, or diatomic oxygen, or sulfur trioxide, or a    combination thereof with water to form sulfuric acid.-   5. The process of embodiment 4 which further comprises reacting said    formed sulfuric acid with zinc chloride.-   6. The process of embodiment 1 wherein said ammonia comprises    gaseous ammonia and wherein said water comprises gaseous water    vapor.-   7. The process of embodiment 6 which further comprises condensing    said gaseous water vapor.-   8. The process of embodiment 6 which further comprising condensing    said gaseous ammonia and said gaseous water vapor.-   9. The process of embodiment 1 wherein at least a portion of the    zinc chloride, the zinc sulfate, or both are in a solid phase.-   10. The process of embodiment 1 wherein at least a portion of    sulfuric acid, hydrochloric acid, or both are in a liquid phase.-   11. The process of embodiment 1 which further comprises separating    at least a portion of zinc sulfate from at least a portion of    hydrochloric acid.-   12. The process of embodiment 1 wherein at least a portion of the    formed zinc sulfate, or of the formed zinc chloride, or the    combination thereof are dissolved in the hydrochloric acid and    wherein the process further comprises separating at least a portion    of (1) the dissolved zinc sulfate or (2) the dissolved zinc    chloride, or (3) the combination of (1) and (2) from the    hydrochloric acid.-   13. The process of embodiment 12 wherein said separating comprises    employing a membrane based process, distillation, electrodialysis,    ion exchange, crystallization, precipitation, ‘salting-out’,    common-ion effect, or a combination thereof-   14. The process of embodiment 1 wherein said reacting of ammonium    chloride with zinc oxide is conducted at a temperature of greater    than about 200° C. and wherein both the ammonium chloride and zinc    oxide are in solid form.-   15. The process of embodiment 1 wherein said reacting of ammonium    chloride with zinc oxide is conducted at a temperature of greater    than about 200° C. and wherein the ammonium chloride comprises a    gaseous mixture of ammonia and hydrochloric acid.-   16. The process of embodiment 1 wherein said reacting of ammonium    chloride with zinc oxide is conducted at a temperature greater than    or equal to about 338° C. and wherein the ammonium chloride    comprises a gaseous mixture of ammonia and hydrochloric acid.-   17. The process of embodiment 1 wherein said reacting of ammonium    chloride with zinc oxide is conducted in a low diatomic oxygen    environment.-   18. The process of embodiment 17 wherein said low diatomic oxygen    environment comprises a diatomic oxygen concentration of less than    about 1 percent by volume.-   19. The process of embodiment 1 wherein the ammonium chloride is    sourced from a process for producing sodium bicarbonate or sodium    carbonate.-   20. The process of embodiment 1 which further comprises producing    sodium bicarbonate or sodium carbonate using a process employing the    ammonia, water, or a combination thereof.-   21. A process comprising:    -   reacting sodium chloride with ammonia, carbon dioxide, and water        to form sodium bicarbonate and ammonium chloride;    -   reacting ammonium chloride with zinc oxide to form zinc        chloride, ammonia, and water;    -   reacting the zinc chloride with sulfuric acid to form zinc        sulfate and hydrochloric acid; and    -   decomposing the zinc sulfate to produce zinc oxide.-   22. The process of embodiment 21 wherein the decomposing of zinc    sulfate further comprises forming sulfur dioxide, or diatomic    oxygen, or sulfur trioxide, or a combination thereof-   23. The process of embodiment 22 which further comprises reacting    said formed sulfur dioxide, or formed diatomic oxygen, or formed    sulfur trioxide, or a combination thereof with water to produce    sulfuric acid.-   24. The process of embodiment 23 which further comprises reacting    said produced sulfuric acid with zinc chloride to form zinc sulfate    and hydrochloric acid.-   25. The process of embodiment 21 which further comprises decomposing    said formed sodium bicarbonate to form carbon dioxide and (1) sodium    carbonate, or (2) sodium sesquicarbonate, or (3) a combination    of (1) and (2).-   26. The process of embodiment 25 which further comprises reacting    the formed carbon dioxide with sodium chloride, ammonia, and water    to form sodium bicarbonate and ammonium chloride.-   27. The process of embodiment 21 which further comprises recycling    said formed gaseous ammonia, gaseous water vapor, or both.-   28. The process of embodiment 21 which further comprises dissolving    said formed sodium bicarbonate in the ocean.-   29. The process of embodiment 25 which further comprises dissolving    said formed sodium carbonate, said formed sodium sesquicarbonate, or    both in the ocean.-   30. The process of embodiment 21 which further comprises employing    carbon dioxide captured from at least one carbon dioxide emission    source, from air, or both.-   31. A process for producing ammonia from ammonium chloride    comprising:    -   thermally decomposing ammonium chloride into a gaseous mixture        comprising ammonia and hydrochloric acid; and    -   contacting said gaseous mixture with zinc oxide, forming solid        zinc chloride, gaseous ammonia, and gaseous water vapor.-   32. A process for producing separated ammonia and hydrochloric acid    from ammonium chloride comprising:    -   reacting ammonium chloride with zinc oxide, forming zinc        chloride, gaseous ammonia, and gaseous water vapor;    -   reacting zinc chloride with sulfuric acid, forming zinc sulfate        and hydrochloric acid; and    -   thermally decomposing zinc sulfate to produce zinc oxide.

1. A process comprising: reacting ammonium chloride with zinc oxide toform a zinc chloride, ammonia, and water; reacting the zinc chloridewith sulfuric acid to form a zinc sulfate and hydrochloric acid; andthermally decomposing the zinc sulfate to produce zinc oxide.
 2. Theprocess of claim 1 wherein the thermal decomposing of zinc sulfatefurther produces sulfur dioxide, or diatomic oxygen, or sulfur trioxide,or a combination thereof.
 3. The process of claim 1 wherein the thermaldecomposing of zinc sulfate further produces sulfur dioxide and whereinthe process further comprises reacting sulfur dioxide with diatomicoxygen to produce sulfur trioxide.
 4. The process of claim 2 whichfurther comprises reacting said sulfur dioxide, or diatomic oxygen, orsulfur trioxide, or a combination thereof with water to form sulfuricacid.
 5. The process of claim 4 which further comprises reacting saidformed sulfuric acid with zinc chloride.
 6. The process of claim 1wherein said ammonia comprises gaseous ammonia and wherein said watercomprises gaseous water vapor.
 7. The process of claim 6 which furthercomprises condensing said gaseous water vapor.
 8. The process of claim 6which further comprising condensing said gaseous ammonia and saidgaseous water vapor.
 9. The process of claim 1 wherein at least aportion of the zinc chloride, the zinc sulfate, or both are in a solidphase.
 10. The process of claim 1 wherein at least a portion of sulfuricacid, hydrochloric acid, or both are in a liquid phase.
 11. The processof claim 1 which further comprises separating at least a portion of zincsulfate from at least a portion of hydrochloric acid.
 12. The process ofclaim 1 wherein at least a portion of the formed zinc sulfate, or of theformed zinc chloride, or the combination thereof are dissolved in thehydrochloric acid and wherein the process further comprises separatingat least a portion of (1) the dissolved zinc sulfate or (2) thedissolved zinc chloride, or (3) the combination of (1) and (2) from thehydrochloric acid.
 13. The process of claim 12 wherein said separatingcomprises employing a membrane based process, distillation,electrodialysis, ion exchange, crystallization, precipitation,‘salting-out’, common-ion effect, or a combination thereof.
 14. Theprocess of claim 1 wherein said reacting of ammonium chloride with zincoxide is conducted at a temperature of greater than about 200° C. andwherein both the ammonium chloride and zinc oxide are in solid form. 15.The process of claim 1 wherein said reacting of ammonium chloride withzinc oxide is conducted at a temperature of greater than about 200° C.and wherein the ammonium chloride comprises a gaseous mixture of ammoniaand hydrochloric acid.
 16. The process of claim 1 wherein said reactingof ammonium chloride with zinc oxide is conducted at a temperaturegreater than or equal to about 338° C. and wherein the ammonium chloridecomprises a gaseous mixture of ammonia and hydrochloric acid.
 17. Theprocess of claim 1 wherein said reacting of ammonium chloride with zincoxide is conducted in a low diatomic oxygen environment.
 18. The processof claim 17 wherein said low diatomic oxygen environment comprises adiatomic oxygen concentration of less than about 1 percent by volume.19. The process of claim 1 wherein the ammonium chloride is sourced froma process for producing sodium bicarbonate or sodium carbonate.
 20. Theprocess of claim 1 which further comprises producing sodium bicarbonateor sodium carbonate using a process employing the ammonia, water, or acombination thereof.
 21. A process comprising: reacting sodium chloridewith ammonia, carbon dioxide, and water to form sodium bicarbonate andammonium chloride; reacting ammonium chloride with zinc oxide to formzinc chloride, ammonia, and water; reacting the zinc chloride withsulfuric acid to form zinc sulfate and hydrochloric acid; anddecomposing the zinc sulfate to produce zinc oxide.
 22. The process ofclaim 21 wherein the decomposing of zinc sulfate further comprisesforming sulfur dioxide, or diatomic oxygen, or sulfur trioxide, or acombination thereof.
 23. The process of claim 22 which further comprisesreacting said formed sulfur dioxide, or formed diatomic oxygen, orformed sulfur trioxide, or a combination thereof with water to producesulfuric acid.
 24. The process of claim 23 which further comprisesreacting said produced sulfuric acid with zinc chloride to form zincsulfate and hydrochloric acid.
 25. The process of claim 21 which furthercomprises decomposing said formed sodium bicarbonate to form carbondioxide and (1) sodium carbonate, or (2) sodium sesquicarbonate, or (3)a combination of (1) and (2).
 26. The process of claim 25 which furthercomprises reacting the formed carbon dioxide with sodium chloride,ammonia, and water to form sodium bicarbonate and ammonium chloride. 27.The process of claim 21 which further comprises recycling said formedgaseous ammonia, gaseous water vapor, or both.
 28. The process of claim21 which further comprises dissolving said formed sodium bicarbonate inthe ocean.
 29. The process of claim 25 which further comprisesdissolving said formed sodium carbonate, said formed sodiumsesquicarbonate, or both in the ocean.
 30. The process of claim 21 whichfurther comprises employing carbon dioxide captured from at least onecarbon dioxide emission source, from air, or both.